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Structural Properties of Nanoclusters: Energetic, Thermodynamic, and Kinetic Effects
Structural Properties of Nanoclusters: Energetic, Thermodynamic, and Kinetic Effects
The structural properties of free nanoclusters are reviewed. Special attention is paid to the interplay
of energetic, thermodynamic, and kinetic factors in the explanation of cluster structures that are
actually observed in experiments. The review starts with a brief summary of the experimental methods
for the production of free nanoclusters and then considers theoretical and simulation issues, always
discussed in close connection with the experimental results. The energetic properties are treated first,
along with methods for modeling elementary constituent interactions and for global optimization on
the cluster potential-energy surface. After that, a section on cluster thermodynamics follows. The
discussion includes the analysis of solid-solid structural transitions and of melting, with its size
dependence. The last section is devoted to the growth kinetics of free nanoclusters and treats the
growth of isolated clusters and their coalescence. Several specific systems are analyzed.
example, Henry, 1998兲, because of the very favorable out by some kind of simulation. In the words of Marks
surface/volume ratio of nanoclusters. More recently, 共1994兲 “small particle structures cannot be understood
there have been developments towards biological uses. purely from experimental data, and it is necessary to
For example, gold nanoparticles studded with short seg- simultaneously use theoretical or other modeling.” The
ments of DNA 共Alivisatos et al., 1996; Mirkin et al., discussion of theoretical and simulation results will
1996兲 could form the basis of an easy-to-read test to make frequent reference to the experiments.
single out genetic sequences 共Alivisatos, 2001兲. Some ap- We cannot pretend to be exhaustive on the subjects of
plications of nanoclusters have a much older history. It our review, since thousands of articles about nanoclus-
has been recently discovered 共Borgia et al., 2002; ters have been produced in the last decade. Some fasci-
Padeletti and Fermo, 2003兲 that the Renaissance masters nating fields, for example, the field of binary clusters and
in Umbria, Italy, used nanoparticles in the decoration of nanoalloys, whose properties depend crucially not only
majolicas with lustre. Lustre consists of a thin film con- on size but also on composition, are completely left out
taining silver and copper clusters with diameters up to a for space reasons. But even on the topics that we explic-
few tens of nanometers, often of noncrystalline struc- itly treat we do not claim to be exhaustive. If some con-
ture. Due to the inclusion of these nanoparticles, lustre tributions have been left out, we apologize in advance.
gives beautiful iridescent reflections of different colors. The review is structured as follows. In Sec. II we give
The starting point for an understanding of cluster a brief description of the methods for free-cluster pro-
properties is the study of their structure. With this goal duction. In Sec. III we deal with the energetics of free
in mind, the first question to answer is the following: nanoclusters, describing general trends, modeling the el-
Given size and composition, what is the most stable clus- ementary interactions, and finding the global minima of
ter structure from an energetic point of view? To answer the PES. In Sec. IV we consider the thermodynamics of
to this question we need to find the global minimum on nanoclusters, focusing on the possibility of solid-solid
the potential-energy surface 共PES兲 of the cluster 共Wales, transitions at finite temperature and on the melting tran-
2003兲. The PES is the product of the elementary inter- sition. Finally Sec. V treats the growth kinetics of nano-
actions among the cluster constituents. clusters, which may take place either in the liquid or in
Once the answer to this first question is given, a sec- the solid state, and the coalescence of nanoclusters. In
ond one arises: What is the effect of raising the tempera- each part, specific systems are treated in details.
ture on the structural properties of a cluster? The study
of this question introduces us to a fascinating field, the II. EXPERIMENTAL METHODS FOR FREE-NANOCLUSTER
thermodynamics of finite systems. PRODUCTION
Finally, the experimental time scales of cluster pro-
duction are often short with respect to the time scales of The experimental methods for producing free nano-
morphology transitions. This leads to a third important clusters have been reviewed by de Heer 共1993兲 and more
question: What are the kinetic effects in the formation recently by Milani and Iannotta 共1999兲 and Binns 共2001兲.
of nanoclusters? To answer to this question, the cluster Here we present a brief summary, focusing on those as-
growth process must be analyzed. pects 共such as the time scale of free-nanocluster growth兲
In this review, we try to summarize and discuss the most closely related to the subjects treated below.
present knowledge about these three points and, to the Sources producing free beams of nanoscale clusters
best of our ability, to answer the above questions con- were made available about 30 years ago for the produc-
cerning the behavior of free clusters. Two general results tion of noble-gas clusters 共Raoult and Farges, 1973兲 and
can, however, be anticipated. more than 20 years ago for producing metallic clusters
First, what clearly emerges from the comparison of 共Sattler et al., 1980; Dietz et al., 1981兲; more recent de-
experimental and theoretical results is that all three fac- velopments have made available sources that are ultra-
tors, energetics, thermodynamics, and growth kinetics of high vacuum compatible, that can produce binary clus-
nanoclusters, must be taken into account when analyz- ters 共Rousset et al., 1996; Cottancin et al., 2000兲, and that
ing realistic situations. Second, interactions among the incorporate extremely efficient mass-selection tech-
constituent particles must be understood in terms of the niques 共see Binns, 2001, and references therein兲.
basic concepts of range and type. The interaction range In most cases, the heart of a cluster source is a region
rules the behavior of systems with pair potentials 共see, where a supersaturated vapor of the material forming
for example, Wales, 2003兲. In systems characterized by the clusters is produced. The first step in cluster produc-
interactions with strong many-body character, metals, tion is the heating of the material to obtain a hot vapor.
for example, other factors come into play together with This can be done in different ways, for example, by heat-
the interaction range, namely, the bond-order/bond- ing up a piece of bulk material in a crucible 共as in seeded
length correlation and the directionality of the interac- supersonic nozzle and inert-gas aggregation sources兲, or
tions. by hitting a target with a laser pulse or an ion beam
The focus of this review article is on theoretical and 共laser evaporation and ion sputtering sources兲. To obtain
simulation issues in free-cluster science. We remark that supersaturation, the hot vapor must be cooled down.
cluster science is a field in which the interplay among There are essentially two ways to achieve this. The first
experiments, theory, and simulations is very active: in is by means of a supersonic expansion 共as in seeded su-
fact, the analysis of an experiment is very often carried personic nozzle sources, where the material is mixed
with a high-pressure inert gas and then expanded兲, squared modulus of the Fourier transform of the scatter-
which causes an adiabatic cooling 共Anderson and Fenn, ers with respect to the momentum transfer q, one builds
1985兲. Hot clusters are usually produced at temperatures a theoretical diffraction pattern by weighting contribu-
close to the evaporation limit 共Bjørnholm et al., 1991兲. In tions from clusters of different structures. In fact, one
the second way, the hot vapor is mixed with a cold inert- can expect that, for example, an icosahedron has a dif-
gas flow, which acts as a collisional thermostat. This ferent Fourier transform than a part of an fcc lattice.
method is used in inert-gas aggregation sources to pro- The geometry is obtained directly by fitting the weights
duce very cold metallic clusters. Here, due to the low of the different structures to the experimental data. On
temperature of the inert gas, cluster production pro- the other hand, information on the size can be obtained
ceeds mainly by the addition of single atoms, and re- from the width of the diffraction rings, because the
evaporation is negligible 共de Heer, 1993兲. When growth larger the cluster, the narrower the diffraction rings. The
ceases, the clusters can be further reheated or cooled more scatterers add their contributions coherently, the
down by subsequent stages of contact with gas at differ- sharper the resulting pattern. Finally, information about
ent temperatures. the cluster temperature is contained in the temperature
What are the typical time scales of nanocluster pro- dependence of the scattered intensity
duction? This question is extremely important, because,
as we see in the following, the finite lifetime of free clus- I共T兲 = I共T=0兲e−2W . 共2兲
ters in flight may cause their trapping into metastable Here W is the Debye-Waller factor,
structures. Let us consider an inert-gas aggregation
source for noble-metal clusters 共Reinhard, Hall, Ugarte, 1
W = 具u2典q2 , 共3兲
and Monot, 1997; Reinhard et al., 1998; Koga and Sug- 3
awara, 2003兲. There, the typical metal vapor tempera-
where 具u2典 is the mean-square vibrational amplitude of
ture Tv and pressure pv are of the order of 1000– 1500 K
the cluster atoms. For harmonic vibrations, 具u2典 ⬀ T.
and 1 – 10 mbar, respectively. Consider now a growing
nanocluster, say with a radius R of 1 nm, which can cor-
respond to 100–200 atoms. If we assume a spherical clus- III. ENERGETICS OF FREE NANOCLUSTERS
ter, the kinetic theory of gases gives for the atomic flux
⌽v 共i.e., the number of metal atoms per second hitting At low temperatures, the most favored structure of a
the cluster surface兲 cluster of N particles is the one that minimizes its total
energy. For example, in atomic clusters, the most fa-
pvAeff vored structure is the global minimum of the potential
⌽v = 共1兲
冑2 m v k B T v , energy as a function of the coordinates of the atomic
cores 共the potential-energy surface or PES兲. Tradition-
where Aeff = 4R2, and mv is the mass of the atoms. This ally, great effort has been devoted to finding reliable
gives ⌽v ⬃ 107 s−1, corresponding to an interval between methods for calculating the total energy, and searching
depositions dep = ⌽−1 for local and global minima. This task implies the fol-
v ⬃ 10 ns. Thus a cluster of 10 at-
2 3
2
See Raoult et al. 共1989b兲, Cleveland and Landman 共1991兲,
Uppenbrink and Wales 共1992兲, Turner et al. 共2000兲, Doye et al. FIG. 8. Phase diagram for Morse clusters: The lines separate
共2001兲, Baletto, Ferrando, et al. 共2002兲, Doye and Hendy 共2003兲 domains pertaining to different structural motifs. Figure cour-
and Sec. III.E for details on some specific systems. tesy of Jonathan Doye.
Electronic shell closing has been extremely successful IV.B.3兲, plays a crucial role. The major evidence for elec-
in explaining the observed experimental abundances of tronic shell closing is for small alkali-metal clusters
alkali-metal clusters, like those found in the seminal ex- 共Knight et al., 1984; Bjørnholm et al., 1990; Nishioka et
periments of Knight et al. 共1984兲 on sodium clusters. In al., 1990兲. For these systems, several calculations 共Röth-
this framework, a cluster is modeled as a super-atom; lisberger and Andreoni, 1991; Spiegelman et al., 1998;
valence electrons are delocalized in the cluster volume Solov’yov et al., 2002兲 indicate that electronic shell clos-
and fill discrete energy levels. There are several degrees ing is a better criterion than atomic packing for deter-
of sophistication of this model. Detailed accounts can be mining the most stable clusters. For larger alkali clusters
found in the reviews by Brack 共1993兲 and de Heer the situation is more complicated. In fact, Martin et al.
共1993兲; a simple and very clear discussion is found in 共1991a兲 and Martin 共1996, 2000兲 have shown that Na
Johnston 共2002兲. Here we briefly sketch only the spheri- clusters, after presenting electronic magic numbers up to
cal jellium model. 2000 atoms, reveal a series of geometric magic numbers
The spherical jellium model assumes a uniform back- at larger sizes 共see Fig. 9兲. This would correspond to a
ground of positive charge, in which electrons move and transition from liquid to solid clusters at increasing size.
are subjected to an external potential. The simplest Moreover, when solid Na clusters are heated and
forms of the potential are the infinitely deep spherical melted, geometric magic numbers disappear to the ad-
well and the harmonic well. The solution of the single- vantage of electronic magic numbers. The same kind of
electron Schrödinger equation for the spherical well behavior was also found for aluminum clusters 共Martin
gives the following series of magic numbers: 2, 8, 18, 20, et al., 1992; Baguenard et al., 1994兲. Therefore the indi-
34, 40, 58,…, etc. On the other hand, the harmonic well cation is that electronic shells are seen when hot liquid
gives the series: 2, 8, 20, 40, 70,…, etc. The experimental clusters are produced, while geometric shells are exhib-
spectra of Knight et al. 共1984兲 reveal high peaks at 8, 20, ited by cold, solid clusters 共Johnston, 2002兲. In small
40 in agreement with both models. There are, however, clusters, both electronic and geometric effects can play
less evident peaks at 18 and 58, which appear only in the important roles, as Zhao et al. 共2001兲 have shown in their
spherical well. Experiments on larger sodium clusters tight-binding global optimization study of Ag clusters at
have revealed electronic shells in these clusters, up to N 艋 20. In conclusion, the interplay of electronic and
about 2000 atoms 共Martin et al., 1991a; Martin, 1996, geometric shell effects, depending on material and size,
2000兲, and in other metals; see, for example, Johnston remains to be fully understood.
共2002兲.
Candidates for observing electronic shell effects are C. Calculation of the total energy of nanoclusters
the metals with weakly bound valence electrons, prima-
rily the alkali and then the noble metals. It seems also A key point in the theoretical study of clusters is the
that the temperature T, which determines whether the choice of an appropriate energetic model. This depends
cluster is solid or liquid depending on N 共see Sec. on the material and the size of the cluster, as well as on
the physical and chemical properties one wishes to in- quantum Monte Carlo calculations in ordering the dif-
vestigate. To cover and illustrate in detail all the meth- ferent isomers of the Si20 cluster, even though there are
ods used in theoretical cluster science would require an still some quantitative differences.
entire book, and it is well beyond the scope of our re- Density-functional calculations can be inserted into a
view. Here we mention only the main methods, trying to molecular-dynamics procedure to give the ab initio mo-
give an idea of their underlying philosophy and range of lecular dynamics. The best known example is the Car-
applicability. Parrinello method 共Car and Parrinello, 1985兲, which
As pointed out in the review by Bonacić-Koutecký et could be well suited to the investigation of thermody-
al. 共1991兲, even clusters of a few atoms are very compli- namic and kinetic properties at T ⬎ 0 K.
cated systems. Indeed, the complexity of quantum me- Even though density-functional methods are nowa-
chanics forces one to employ approximate methods. days reliable and efficient for a large variety of systems,
The ab initio methods of quantum chemistry 关Hartree- there is still a great interest in developing methods re-
Fock and post Hartree-Fock; see Bonacić-Koutecký et quiring a smaller computational effort. In fact, global
al. 共1991兲, and references therein兴 were extensively ap- optimization 共see Sec. III.D兲 of clusters in the frame-
plied to the study of small clusters about 20 years ago. work of ab initio calculations is not feasible at present
For example, small-size 共2 艋 N 艋 9兲 Li and Na clusters except for a few systems and at very small sizes. More-
contain relatively few electrons, so that all-electron cal- over, ab initio molecular dynamics is limited to small
culations were possible 共Boustani et al., 1987兲. When ei- systems on short time scales, so that both the accurate
ther the size of the cluster or the nuclearity of the atoms sampling of thermodynamic properties and the simula-
increase, these methods become cumbersome, and at tion of kinetic processes 共diffusion, structural transfor-
present they are less commonly employed than in the mations, growth兲 are far beyond present capabilities.
past. Therefore several approximate energetic models for
Methods based on density-functional theory 共Hohen- clusters have been developed, often on semiempirical
berg and Kohn, 1964; Kohn and Sham, 1965兲, when ad- grounds. At an intermediate degree of computational
equately tested, can be of very high accuracy and less effort, there is the tight-binding model for semiconduc-
cumbersome from the computational point of view, tors 共Ho et al., 1998兲 and metals 共Barreteau, Guirado-
making it possible to treat a wide variety of systems and Lopez, et al., 2000; Bobadova-Parvanova et al., 2002兲.
somewhat larger sizes. Calculations on metals up to a This allows global optimization searches for clusters of a
few hundred atoms are present in the literature, even for few tens of atoms, and molecular-dynamics simulations
difficult systems such as the transition and noble metals even for clusters of 102 atoms 共Yu et al., 2002兲, even
共see, for example, Häberlen et al., 1996; Jennison et al., though on rather short time scales.
1997; Garzón, Michaelian, et al., 1998; Fortunelli and Larger sizes and longer time scales can be now treated
Aprà, 2003; Nava et al., 2003兲. The weak point in by classical atom-atom 共or even molecule-molecule兲 po-
density-functional calculations is often the exchange and tentials, which are built up on the basis of approximate
correlation term, which is treated in an approximate quantum models. These potentials contain parameters
way. The validity of the treatment depends on the sys- fitted to experimental material properties 共semiempirical
tems and has to be checked each time. The simplest ap- potentials兲 or to density-functional calculations 关ab-
proximation is the local-density approximation; more so- initio-based potentials 共Kallinteris et al., 1997; Garzón,
phisticated approaches include gradient corrections Kaplan, et al., 1998兲兴. For metallic systems, several atom-
共very important in transition and noble metals兲, which atom potentials have been developed, such as
are often called the generalized gradient approximation. embedded-atom 共Daw and Baskes, 1984; Voter, 1993兲,
At this level, different exchange and correlation func- glue 共Ercolessi et al., 1988兲, second-moment tight-
tionals are available 共see Perdew and Wang, 1986; binding 共Gupta, 1981; Rosato et al., 1989兲, Sutton-Chen
Becke, 1988, 1996; Perdew et al., 1992, 1996兲. In order to 共Sutton and Chen, 1990兲, and effective-medium 共Jacob-
check the validity of gradient-corrected density- sen et al., 1987兲 potentials. A discussion of the criteria
functional calculations, Mitás et al. 共2000兲 performed for fitting the parameters in Gupta 共1981兲 potentials is
quantum Monte Carlo simulations 共Ceperley, 1994兲 on found in López and Jellinek 共1999兲. For metals, these
small-size silicon clusters. In quantum Monte Carlo, potentials must contain a many-body term, which is re-
which is computationally very demanding, many-body sponsible for the correct surface relaxations 共Desjon-
correlations are directly taken into account by an ex- queres and Spanjaard, 1998兲. The advantage of this ap-
plicit correlation in the trial wave function. It turned out proach is that it allows full global optimization to sizes
that there were significant discrepancies between the of the order of ⬃200 atoms, local relaxation of clusters
density-functional 共with different types of exchange and of ⬃105 atoms, and molecular-dynamics simulations on
correlation functionals兲 and the quantum Monte Carlo time scales of 10 s and more for clusters of 102 atoms,
results. Mitás et al. 共2000兲 confirmed the already known quite close to the growth time scales of free clusters in
bias of density-functional calculations towards compact inert-gas aggregation sources. The disadvantage is that
structures; this bias is very strong at the level of the even the qualitative accuracy of these potentials is often
local-density approximation, and considerably reduced questionable, and they must be tested carefully before
if gradient corrections are included. There are some being used 共see, for example, Ala-Nissila et al., 2002兲. As
functionals that give the same qualitative results as the we shall see in the following, there are several systems
generation are compared to the sons via their fitness, Another popular algorithm is simulated annealing
and a new generation is formed from the old individuals 共Kirkpatrick et al., 1983; Biswas and Hamann, 1986;
and the sons, by some rule, which always includes the Freeman and Doll, 1996兲. In thermal simulated anneal-
best-fit individual in the new generation. Very often, sev- ing, the system is evolved at constant high T on the un-
eral populations are evolved in parallel, and individuals transformed PES by either Monte Carlo or molecular
are exchanged between them from time to time. In a dynamics, then slowly cooled down. Simulated anneal-
genetic algorithm, task 共b兲 is accomplished by chromo- ing has the advantage of being pretty much physical: one
some mixing and mutations and by exchanges of indi- tries to mimic the procedure of cooling a sample which
viduals between subpopulations, while task 共a兲 corre- hopefully will reach its most stable configuration if cool-
sponds to comparing the fitness of the individuals after a ing is sufficiently slow. This algorithm is easily incorpo-
local minimization on them, i.e., comparing Ũ共sons兲 to rated into standard Monte Carlo and molecular-
dynamics codes 共including ab initio molecular dynamics兲,
Ũ共parents兲. Recent developments include similarity
and the analysis of its output is easy and intuitive. For
checking among cluster structures to keep the diversity
these reasons, this algorithm has been used for a large
of the population as the genetic optimization goes on, as
in Cheng et al. 共2004兲. The use of genetic algorithms in variety of systems.4 There is, however, a major drawback
cluster optimization was pioneered by Hartke 共1993兲 and to simulated annealing: it utilizes effectively a single lo-
by Xiao and Williams 共1993兲, who made applications to cal optimization, and if the system fails to be confined to
Si4 and various molecular clusters, respectively. Their the basin of attraction of the global minimum as the
work was followed by applications to a wide variety of temperature is decreased, the algorithm may fail, even if
systems. Michaelian et al. 共1999兲 optimized transition it passed through the basin of the global minimum when
and noble-metal clusters by a symbiotic variant of a ge- T was high. As a result, simulated annealing is less effi-
netic algorithm 共Michaelian, 1998兲. Hartke 共2000, 2003兲 cient than genetic and basin-hopping algorithms
also treated water clusters; Deaven and Ho 共1995兲, 共Hartke, 1993; Zeiri, 1995兲. To avoid trapping in a single
Deaven et al. 共1996兲, and Ho et al. 共1998兲 optimized basin, one can make long high-T Monte Carlo or
Lennard-Jones and silicon clusters; Rata et al. 共2000兲 and molecular-dynamics runs, collecting a large quantity of
Bobadova-Parvanova et al. 共2002兲 considered silicon and different snapshots and quenching them down 共Sebetci
iron clusters; Darby et al. 共2002兲, Massen et al. 共2002兲, and Güvenc, 2003; Baletto et al., 2004兲, monitoring the
Bailey et al. 共2003兲, and Lloyd et al. 共2004兲 optimized short-term average of kinetic energy 共Jellinek and
Pd-Pt, Au-Cu, and Al-Ni nanoalloy clusters; finally Garzón, 1991; Garzón and Posada-Amarillas, 1996兲. T
Rossi et al. 共2004兲 searched for the global minima of must be chosen carefully. If it is too high, the probability
Ag-Cu, Ag-Ni, and Ag-Pd clusters. Recent reviews are of catching the global minimum is very small; if T is too
those of Hartke 共2002兲 and Johnston 共2003兲. low, the cluster is likely to remain trapped in the basin it
The basin-hopping algorithm 共Li and Scheraga, 1987; starts from.
Doye and Wales, 1998a; Doye, 2004兲 differs from genetic Another family of annealing algorithms is known as
algorithms because it accomplishes task 共b兲 simply by a quantum annealing 共Amara et al., 1993; Finnila et al.,
canonical Monte Carlo simulation at constant T on the 1994; Freeman and Doll, 1996兲. In quantum annealing,
transformed PES. In this framework, the transformation the system is first collapsed into its quantum ground
of the PES amounts to lowering the barriers between state by using diffusion or Green’s-function Monte Carlo
basins to the maximum possible extent, while keeping techniques 共Ceperley, 1994兲 and then quantum mechan-
the levels of the minima unchanged. Starting from a ics is slowly turned off. This algorithm utilizes delocal-
given basin, a move with random displacements is tried, ization and tunneling as the primary means for avoiding
and the energy difference between the new and the old trapping in metastable states. Amara et al. 共1993兲 and
position ⌬Ũ is calculated. If ⌬Ũ ⬍ 0 the move is ac- Finnila et al. 共1994兲 applied quantum annealing to
cepted with probability 1, otherwise with probability Lennard-Jones clusters up to N = 19. Lee and Berne
共2000兲 coupled quantum and thermal annealing, being
exp关−⌬Ũ / 共kBT兲兴. On Ũ, transitions can occur in any di- thus able to find the fcc global minimum of the Lennard-
rection, not only through saddle points, and transitions Jones cluster of size 38, but this approach failed for
to lower-lying minima are always accepted. Basin hop-
other difficult cases at larger size, such as the Marks
ping has been applied successfully to the optimization of
decahedron at N = 75. Recently, Liu and Berne 共2003兲
a large variety of systems, from Lennard-Jones clusters
have developed a new quantum annealing procedure,
共Wales and Doye, 1997兲 to clusters of fullerene mol-
based on quantum staging of path-integral Monte Carlo
ecules 共Doye et al., 2001兲, of transition and noble metals
sampling and local minimization of individual imaginary
共Doye and Wales, 1998b兲, and of aluminum 共Doye,
time slices. This method is able to locate all Lennard-
2003兲. Basin hopping was able to find the difficult puta-
tive global minima in Lennard-Jones clusters at sizes 38,
75, 76, 77, and 98, starting from random initial condi- 4
To cite but a few, Jones 共1991兲, Kumar and Car 共1991兲, Röth-
tions. Recently, Lai et al. 共2002兲 optimized sodium clus- lisberger and Andreoni 共1991兲, Jones and Seifert 共1992兲, Stave
ters by both genetic and basin-hopping algorithms, find- and DePristo 共1992兲, Vlachos et al. 共1992兲, Cheng et al. 共1993兲,
ing the same set of minima. This could indicate that both Christensen and Cohen 共1993兲, Jones 共1993兲, Ma and Straub
algorithms have comparable efficiency. 共1994兲, Ahlrichs and Elliott 共1999兲, Bacelo et al. 共1999兲.
Jones minima for N 艋 100 except at N = 76, 77, 98, being creases with increasing potential energy, thus stabilizing
thus comparable to basin-hopping and genetic algo- the lower energy states and broadening the thermody-
rithms. This form of quantum annealing uses local mini- namics. The transformation to a staircase PES is not the
mization to accomplish task 共a兲, and mutations 共in which only useful transformation. Other possibilities have been
coordinates of randomly selected atoms are reset兲 to fa- suggested by Pillardy and Piela 共1995兲, Locatelli and
cilitate task 共b兲. Schoen 共2003兲, and Shao et al. 共2004兲.
An algorithm that tries to combine the advantages of What are the maximum sizes presently tractable by
simulated-annealing, genetic, and basin-hopping ap- global optimization? This answer depends on the system
proaches has been recently developed by Lee et al. under study and on the degree of sophistication of the
共2003兲. Their algorithm was able to optimize Lennard- interaction potential. In the Cambridge Cluster Data-
Jones clusters up to size 201. base 共see www-wales.ch.cam.ac.uk/CCD.html兲, putative
Finally, a very recent proposal is to search for global global minima for several systems are reported, ranging
minima by means of a growth procedure. Solov’yov et al. from Lennard-Jones to Morse, metallic, and water clus-
共2003, 2004兲 applied this method to Lennard-Jones clus- ters. Even for the simplest potentials, the largest sizes
ters, starting from a tetrahedron, and adding one atom are up to N = 190 关for Al 共Doye, 2003兲 and Pb clusters
at a time according to different procedures 共adding an 共Doye and Hendy, 2003兲 modeled by the glue potential
atom on the surface, inside the surface, or at the center 共Lim et al., 1992兲兴, and sizes decrease for more complex
of mass of the cluster兲. After adding a new atom, the interactions. Very recent seeded optimizations of
cluster is quenched down to search for the closest local Lennard-Jones clusters 共Shao et al., 2004兲 reached N
minimum, and the results of the different addition pro- = 330. In order to treat large sizes, Krivov 共2002兲 has
cedures are compared to select the best minimum. This proposed a hierarchical method for optimizing qua-
procedure exploits the fact that clusters of similar sizes siseparable systems. In these systems, distant parts are
are likely to have global minima with some resemblance, independent, so that a perturbation to the coordinates of
and in this respect it is a seeded algorithm. Solov’yov et a given part has very little influence on distant atoms.
al. 共2004兲 were able to find all global minima up to N According to Krivov 共2002兲, one can exploit this prop-
erty to build up a hierarchical procedure that can treat
= 150. Again, their procedure works on Ũ, since clusters Lennard-Jones clusters of several hundreds of atoms.
are compared for selection after local minimization. More complex systems such as water clusters have been
This last observation lead us to a summarizing com- optimized up to N ⯝ 30 共Wales and Hodges, 1998;
ment. The most successful algorithms make extensive Hartke, 2003兲. Ahlrichs and Elliott 共1999兲 optimized alu-
use of local minimization, comparing the structures for minum clusters within a density-functional approach up
selection after having performed that minimization. This to N = 15 by simulated annealing. Tekin and Hartke
amounts effectively to working on Ũ. To use the words 共2004兲 optimized Si clusters by a combination of an em-
of Doye 共2004兲, “the method for searching Ũ is of sec- pirical global search and density-functional local optimi-
ondary importance to the use of the transformation it- zation up to N = 16. In the case of tight-binding modeling
self.” The searching method may be based on thermal of the interactions, the sizes amenable by global optimi-
Monte Carlo, quantum tunneling, or genetic operations, zation approaches extend to a few tens of atoms. See,
but in the end the efficiencies are comparable, given that for example, Zhao et al. 共2001兲, who optimized Ag clus-
the algorithms are well constructed. ters up to N = 20 by a genetic algorithm.
Doye and Wales 共1998a兲 have shown that the transfor- How do the best algorithms scale with cluster size?
This might be an ill-posed question, since there is no
mation to Ũ modifies the thermodynamics of the system demonstration that the minima found by the different
in such a way that the temperature range in which tran- algorithms are really global. However, Liu and Berne
sitions among different funnels are possible is enlarged, 共2003兲 find that their quantum annealing algorithm
and the probability of occupying the basin of the global scales as N3.2 for Lennard-Jones clusters in the size
minimum is increased. This can be understood by ana- range 11–55, and Hartke 共1999兲 finds that his genetic
lyzing the occupation probability of a minimum s. For an algorithm scales approximately as N3, again for
untransformed PES within the harmonic approximation Lennard-Jones clusters up to N = 150.
共see Sec. IV兲 ps ⬀ exp共−Es兲 / ⍀s3N−6, where Es is the
potential energy of minimum s, ⍀s is the geometric
mean vibrational frequency, and  = 共kBT兲−1, with kB the E. Studies of selected systems
Boltzmann constant. For a transformed PES, ps
⬀ As exp共−Es兲, where As is the hyperarea of the basin In this section we review the energetics of atomic clus-
of attraction of minimum s. The differences between ters of some selected materials, chosen both for their
these expressions, the vibrational frequency and hyper- importance from the point of view of basic science 共for
area terms, have opposite effects on the thermodynam- example, noble-gas and alkali-metal clusters, which have
ics. The higher energy minima are generally less rigid been the benchmark for testing theoretical models兲 and
and have a favorable vibrational entropy, so that the for their practical applications 共silicon clusters, transition
transitions are pushed down to lower temperature and and noble-metal clusters兲. Finally, we treat a specific
sharpened. By contrast, the hyperarea of the minima de- kind of molecular cluster, those of fullerene molecules,
whose interpretation in energetic terms has been a long- 共2,2,2兲 and 共2,3,2兲 Marks decahedra, respectively. Later
standing puzzle. on, Leary and Doye 共1999兲 discovered that the global
minimum at N = 98 is tetrathedral. Romero et al. 共1999兲
1. Noble-gas clusters optimized clusters in the range 148艋 N 艋 309 on icosa-
hedral and decahedral lattices, finding again a preva-
Noble-gas clusters have been thoroughly studied since lence of icosahedron putative global minima with only
the early 1980s. Excellent accounts of their properties 11 decahedron exceptions.
are those of Haberland 共1994兲 and Johnston 共2002兲. At larger sizes, Raoult et al. 共1989b兲 compared perfect
Here we briefly review their energetics, focusing on the icosahedron and decahedron structures and concluded
transition sizes among structural motifs and comparing that Marks decahedra finally prevail over icosahedra at
theory with experiment. A special place among noble-
N ⬎ 1600. Concerning the transition to fcc structures,
gas clusters is occupied by He clusters, which are the
Xie et al. 共1989兲 compared icosahedral and cuboctahe-
best known example of quantum clusters. Recently
dral clusters, finding a crossover at N ⬃ 104. However,
there has been a noticeable experimental interest in He
cuboctahedra are not the most favorable fcc clusters.
clusters, which can be formed by 4He, 3He, or a mixture Therefore the crossover should be at much lower sizes
of the two.5 In the following, we treat “classical” clusters 共Raoult et al., 1989a; van de Waal, 1989兲, comparable to
first and then He clusters. the crossover size with Marks decahedra.
In a classical series of electron-diffraction experi- The combination of these energy-minimization results
ments, Farges et al. 共1983, 1986兲 investigated the struc- gives a reasonable interpretation of the experiments,
ture of neutral Ar clusters produced in a free-jet expan- even though there are some points that probably cannot
sion. They compared the experimental diffraction be explained in terms of the energetics alone. At small
patterns with those obtained by freezing Lennard-Jones sizes, the agreement between the global optimization
droplets of different sizes in molecular-dynamics simula- calculations and the experiments is good, even though
tions and were thus able to identify the experimental the decahedron global minima are not yet observed.
products up to N ⬃ 103 atoms. Harris et al. 共1984兲 mea- This may indicate the presence of entropic effects, of the
sured the mass spectra of charged Ar clusters at N kind discussed in Sec. IV.A, or that even at small sizes
⬍ 100. At 20⬍ N ⬍ 50, both experiments found polyi- some kind of kinetic trapping is taking place 共see Sec.
cosahedral structures, composed by interpenetrating 13- V.A兲. At larger sizes, the comparison of theory and ex-
atom icosahedra. From N = 50 to N ⬃ 750 multishell periment is much more difficult, and there has been con-
structures based on the Mackay icosahedron were siderable debate in the interpretation of the diffraction
found. Farges et al. 共1986兲 were also able to single out data in terms of known structures 共van de Waal, 1996兲.
features from diffraction by fcc planes in their spectra of For example, fcc clusters with twin faults give electron
clusters with N ⬎ 600 atoms. Thus they came to the con- diffraction patterns very similar to those of Marks deca-
clusion that the icosahedron→ fcc transition is placed at hedra. In any case, a coarse-grained picture is in agree-
N ⬃ 750. However, in a more recent analysis, van de ment with the general trend of a transition from the
Waal et al. 共2000兲 have shown that the transition is to a icosahedron motif to other structures. A more detailed
mixture of fcc, hcp, and random close-packed regions, analysis reveals that several kinds of clusters can be
with no significant preference for the fcc bulk structure. present in the same size range, so that structural transi-
Let us see how the energetics calculations compare tions are not really sharp. Quantitative agreement on
with these experimental results. Most of the calculations the transition size between the Lennard-Jones calcula-
are based on the use of the Lennard-Jones potential, tions and the experiments has not been reached, prob-
which is a very popular model for noble-gas systems ably due to the limited accuracy of the Lennard-Jones
even though not completely accurate. Several global op- potential for Ar. At present, it is very difficult to ascer-
timization studies have shown that the icosahedron mo- tain whether the diffraction data from large clusters sup-
tif is dominant at small sizes,6 with few exceptions. Poly- port the existence of either entropic or kinetic effects.
icosahedral clusters are formed at sizes 19, 23, and 26 Some interesting results addressing this point 共Ikeshoji
共Farges et al., 1988; Ikeshoji et al., 1996兲. Indeed, Wales et al., 2001兲 are discussed in Sec. V.A.
and Doye 共1997兲 found that there are only seven excep- Let us now consider 4He clusters. While the dimer is
tions in the range 13艋 N 艋 150: at N = 38 the global mini- stable but very weakly bound 共Luo et al., 1993; Grisenti
mum is a truncated octahedron; at N = 75, 76, 77 and N et al., 2000兲, the trimer 关which should have a noticeable
= 102, 103, 104 the best structures are based on the contribution from linear configurations according to the
calculations by Lewerenz 共1996兲兴 and larger clusters are
5
much more stable 共Toennies and Vilesov, 1998兲. Chin
Recent discussions of He clusters are those of Whaley and Krotscheck 共1992兲 calculated the ground-state prop-
共1994兲, Toennies and Vilesov 共1998兲, Scoles and Lehmann
erties of various 4He clusters modeled by the Aziz et al.
共2000兲, Callegari et al. 共2001兲, Northby 共2001兲, Johnston 共2002兲,
Jortner 共2003兲. 共1987兲 potential, considering several sizes up to N = 112,
6
See Hoare and Pal 共1975兲, Farges et al. 共1985兲, Freeman and by diffusion Monte Carlo simulations. They found evi-
Doll 共1985兲, Northby 共1987兲, Wille 共1987兲, Coleman and Shal- dence of density oscillations indicating a possible shell
loway 共1994兲, Xue 共1994兲, Pillardy and Piela 共1995兲, Deaven et structure. Chin and Krotscheck 共1995兲 confirmed the ex-
al. 共1996兲, Wales and Doye 共1997兲, Romero et al. 共1999兲. istence of these oscillations for larger clusters, as well,
and were also able to recover the bulk limit of the exci- 共2003兲. Ishikawa et al. 共2001兲 reanalyze the problem of
tation spectrum. In a very recent experiment Brühl et al. Li6, in which planar and 3D structures were found to be
共2004兲 observed magic sizes at N = 10, 11, 14, 22, 26, 27, in competition, by a global optimization procedure em-
and 44 atoms, in 4He clusters produced in a free-jet ex- ploying the replica exchange method 共Swendsen and
pansion. By comparing the experimental results with dif- Wang, 1986兲 applied to ab initio calculations. They find a
fusion Monte Carlo calculations, Brühl et al. 共2004兲 3D structure of D4h symmetry group, which is slightly
showed that these magic sizes are not related to en- lower in energy than the planar triangle and the pen-
hanced binding energies at specific values of N, but to tagonal pyramid. Poteau and Spiegelmann 共1993兲 per-
the sizes at which excited levels cross the chemical- formed a search for the best Na isomers up to N = 34 by
potential curve and become stabilized. a growth Monte Carlo algorithm in the framework of a
Clusters of 3He are much less stable, because the con- distance-dependent tight-binding 共Hückel兲 model. They
stituent atoms are fermions, so that the minimum num- found that at N = 34 the best isomer is the double icosa-
ber of atoms Nmin needed to form a stable cluster is hedron surrounded by a ring of 15 atoms. Sung et al.
relatively large. A configuration-interaction calculation 共1994兲 optimized Li clusters up to N = 147 by simulated
based on a phenomenological density functional gave annealing within the local spin-density approximation to
Nmin = 29 共Barranco et al., 1997兲, while subsequent varia- the density-functional theory, finding that for 55艋 N
tional Monte Carlo calculations with the Aziz potential 艋 147 the structures based on the Mackay icosahedron
gave 34–35 as an upper bound to Nmin 共Guardiola, 2000; are the lowest in energy. This has been recently con-
Guardiola and Navarro, 2000兲. The same kind of calcu- firmed by Reyes-Nava et al. 共2002兲, who performed a
lations 共Guardiola and Navarro, 2002兲 have recently global genetic optimization of sodium modeled by
been applied to mixed 4He-3He clusters, finding that Gupta 共1981兲 potentials. A thorough global optimization
their stability has a nontrivial dependence on size and study 共by both genetic and basin-hopping algorithms兲 of
composition. Na, K, Rb, and Cs clusters in the framework of the
Gupta potential 共as developed by Li et al., 1998兲 has
2. Alkali-metal clusters
been performed by Lai et al. 共2002兲 up to N = 56. They
found a sequence based on icosahedron clusters except
The structural properties of small Li and Na clusters for N = 36 and N = 38. At N = 38 the global minimum is a
have been the subject of extensive theoretical activity, truncated octahedron, with distorted facets in the cases
following the seminal experiments of Knight et al. of Na and Cs; at N = 36 the structure is a distorted in-
共1984兲. Bonacić-Koutecký et al. 共1991兲 gave an excellent complete truncated octahedron.
account of the earlier developments, which are very The transition from electronic to geometric magic
briefly summarized here. Systematic ab initio numbers in Na clusters has already been discussed in
configuration-interaction studies on Li and Na clusters Sec. III.B. Here we simply recall that for 2000⬍ N
共Boustani et al., 1987; Bonacić-Koutecký et al., 1988兲 for ⬍ 20 000, there is experimental evidence 共Martin et al.,
N 艋 9 have shown a complete analogy between the two 1991a; Martin, 1996, 2000兲 of peaks in the abundances of
elements. The lowest isomers are planar up to the pen- Na clusters at sizes corresponding to the completion of
tamer; at N = 6 a pentagonal pyramid and a triangular perfect icosahedron, Ino decahedron 共Ino, 1969兲, or cub-
planar structure are in very close competition; larger octahedron structures, which have exactly the same
clusters are 3D. In agreement with the experimental magic numbers. From these magic numbers, one cannot
magic numbers and with the electronic shell closing ar- directly infer the actual cluster structures. However,
guments, the cluster of 8 atoms, of tetrahedral symmetry there is at least one indirect argument in favor of icosa-
共Jellinek et al., 1994兲, is especially stable compared to hedral structures: in fact, while complete icosahedra are
neighboring sizes. Röthlisberger and Andreoni 共1991兲 surely more favorable than incomplete ones, Ino deca-
and Röthlisberger et al. 共1992兲 performed Car-Parrinello hedra are not usually the best decahedral structures, nor
calculations on Na at slightly larger sizes. At N = 13, they are cuboctahedra the best among the possible truncated
found that the most stable isomer is neither an icosahe- octahedron clusters.
dron nor a cuboctahedron, but a capped pentagonal bi-
pyramid. At N = 18 the most stable isomer was the
double icosahedron minus one vertex, and at N = 20 the 3. Noble-metal and quasi-noble-metal clusters
isomers based on pentagonal symmetries 共which are Here we treat the energetics of pure clusters of the
closely related to the double icosahedron兲 were found to elements of the last two columns of the transition series:
be more stable than structures with tetrahedral symme- Ni, Cu, Pd, Ag, Pt, and Au. We restrict our treatment to
try. On the other hand, Bonacić-Koutecký et al. 共1991兲 neutral clusters unless otherwise specified.
found that two tetrahedron structures are the lowest in
energy for Li20 and Na20 共Bonacić-Koutecký, Fantucci, et
al., 1993兲. Spiegelman et al. 共1998兲 found results in rea- a. Gold clusters
sonable agreement with the previous calculations by a Small Au clusters 共N 艋 10兲 have been thoroughly
tight-binding approach. treated by ab initio methods. Bravo-Pérez et al. 共1999a兲
Recent developments are discussed by Ishikawa et al. studied sizes 3 艋 N 艋 6, finding that the best structures
共2001兲, Solov’yov et al. 共2002兲, and Matveentsev et al. are planar 共Bravo-Pérez et al., 1999b兲. These results have
TABLE I. Potential parameters and cluster crossover sizes for several metals. Parameters p , q of the Rosato et al. 共1989兲 potential;
parameters 1 = pq / 2, 2, 3, and A 关see Eqs. 共16兲 and 共17兲兴; sizes where ⌬ is minimum 共NIh ⌬ for icosahedra and N⌬ for
Dh
decahedra兲, and crossover sizes 共NIh→Dh, NDh→fcc, and NIh→fcc兲. in the case of the different noble and quasi-noble metals. The
parameters of the potentials are taken from Baletto, Ferrando, et al. 共2002兲 except for those of Ni, which are found in Meunier
共2001兲 and Baletto, Mottet, and Ferrando 共2003兲. The results on the crossover sizes are taken from Baletto, Ferrando, et al. 共2002兲,
except those for Ni which are published here for the first time. The results for A are taken from Soler et al. 共2000兲.
Metal p q 1 2 3 A NIh
⌬ NDh
⌬ NIh→Dh NDh→fcc NIh→fcc
Cu 10.55 2.43 13.1 0.062 0.35 0.24 309 20000 1000 53000 1500
Ag 10.85 3.18 17.2 0.065 0.29 0.54 147 14000 ⬍300 20000 400
Au 10.53 4.30 22.6 0.082 0.16 1.86 147 1300 ⬍100 500 ⬍100
Ni 11.34 2.27 12.9 0.055 0.37 0.05 561 17000 1200 60000 2000
Pd 11.00 3.79 20.9 0.062 0.21 0.78 147 5300 ⬍100 6500 ⬍100
Pt 10.71 3.85 20.6 0.073 0.22 1.40 147 5300 ⬍100 6500 ⬍100
sivated particles of a few nanometer’s diameter, with a Sutton and Chen 共1990兲 potential and optimized Ag
prevalence, however, of 共possibly defected兲 Marks and clusters at N 艋 80, finding the same lowest-energy struc-
Ino decahedra. Defected clusters 2 – 4 nm in diameter tures as Bonacić-Koutecký, Cespiva, et al. 共1993兲 at N
have been detected by x-ray diffraction 共Zanchet et al., = 7 , 8 , 9, and icosahedral global minima at N = 13 and 55.
2000兲. Moreover, in a recent experiment, Koga and Sug- Thirty of the global minima were icosahedral in charac-
awara 共2003兲 have analyzed a large sample of free Au ter, but several decahedron and fcc clusters were found,
clusters obtained in an inert-gas aggregation source, the most stable being at N = 38 共truncated octahedron兲
with diameters of 3 – 18 nm and found that icosahedra
were the most frequent and decahedra second-most fre-
quent, fcc clusters being absent. These results are again
an indication in favor of kinetic effects and are discussed
in Sec. V.B.3.
b. Silver clusters
As in the case of Au, the energetics of Ag clusters
have been the subject of intensive study in all size
ranges. For N 艋 9, Bonacić-Koutecký, Cespiva, et al.
共1993, 1994兲 searched for the lowest-energy clusters by a
self-consistent Hartree-Fock procedure which was able
to produce structures in good agreement with the ex-
periments 共Ganteför et al., 1990; Ho et al., 1990;
Alameddin et al., 1992; Jackschath et al., 1992兲. They
found that the best isomers are planar up to the pen-
tamer, as confirmed by Matulis et al. 共2003兲 by density-
functional calculations. Santamaria et al. 共1994兲 found a
planar structure also at N = 6. Recent density-functional
studies have considered N 艋 12 共Fournier, 2001兲, and N
= 13 共Oviedo and Palmer, 2002兲. The latter study sug-
gested that the best isomer of 13 atoms is of low sym-
metry, and that even the cuboctahedron is more favor-
able than the icosahedron. By contrast, previous density-
functional studies on larger Ag clusters 共Jennison et al.,
1997兲 found that at N = 55 the icosahedron is lower in
energy than the cuboctahedron.
Larger clusters have been studied mainly by semi-
empirical interatomic potentials. This approach has al-
lowed global-minimum searches for N up to 100 atoms FIG. 14. ⌬ as a function of N for different cluster motifs in Ni,
共Doye and Wales, 1998b; Erkoç and Yilmaz, 1999兲 and Cu, Pd, Ag, Pt, and Au: 䊊, iscosahedra; 䊐, decahedra; 䉭,
the comparison of selected magic structures belonging to trunacted octahedra. Data are taken from Baletto, Ferrando,
the icosahedral, decahedral, and truncated octahedral et al. 共2002兲, except for the data concerning Ni, which are origi-
motifs for N up to 40 000 atoms 共Baletto, Ferrando, et nal. For decahedra and truncated octahedra only the most fa-
al., 2002兲. Doye and Wales 共1998b兲 modeled Ag by the vorable clusters are shown in the different size ranges.
and N = 71, 75 共decahedron兲. Mottet et al. 共1997兲 mod- atoms and that decahedron and truncated octahedron
eled Ag by the Rosato et al. 共1989兲 semiempirical poten- structures are in close competition up to 30 000 atoms at
tial, reproducing essentially the same behavior as the least 共see Table I兲. Contrary to the Ag case, this behav-
Sutton and Chen 共1990兲 potential at small sizes. They ior is in agreement with the inert-gas aggregation experi-
showed that clusters of high stability can be obtained by ments of Reinhard, Hall, Berthoud, et al. 共1997, 1998兲,
removing the central atom in perfect icosahedra. In fact, who were able to identify a prevalence of small icosahe-
a central vacancy allows neighboring atoms to better re- dra, intermediate-size decahedra, and large fcc clusters,
lax, expanding their intrashell distance. The same effect with a wide size interval in which decahedra and fcc
was also found in Cu and Au clusters. We note that, at clusters coexisted. The crossover size between icosahe-
variance with Au, there is no indication in Ag in favor of dron and decahedron structures is in agreement with the
disordered structures at geometric magic numbers 共38, calculations.
55, 75兲. Finally Baletto, Ferrando, et al. 共2002兲 and Mot-
tet et al. 共2004兲 looked at the crossover sizes 共see Table I兲
d. Platinum clusters
by an extensive comparison of clusters of the different
motifs. The energetic stability of small Pt clusters has been
All the previous theoretical results agree in predicting addressed by fewer studies than the other metals treated
that Ag follows the general trend outlined in Sec. III.A, here. Grönbeck and Andreoni 共2000兲 performed a
with small icosahedra, intermediate-size decahedra, and density-functional study in the size range 2 艋 N 艋 5, find-
large truncated octahedra clusters. This is in clear con- ing that the lowest-lying isomers are planar for both the
trast with the inert-gas aggregation experiments by tetramer and the pentamer. The preference for planar
Reinhard, Hull, Ugarte, and Monot 共1997兲, in which structures is in agreement with previous density-
small clusters 共⬃2 nm of diameter兲 were mainly decahe- functional calculations by Yang et al. 共1997兲, who also
dral 共or fcc兲 while large clusters 共above 5 nm兲 were found planar structures for N = 6 by a dynamical quench-
mostly icosahedral. This discrepancy can only be ex- ing procedure. In contrast, other ab initio calculations
plained by taking into account kinetic trapping effects 共Dai and Balasubramanian, 1995兲 on the tetramer gave
leading to the growth of metastable structures, as dis- preference to the tetrahedal structure, as in the density-
cussed in Sec. V.B.3. functional results of Fortunelli 共1999兲, who found that
the lowest-lying isomer is indeed the tetrahedron, with a
c. Copper clusters planar rhombic structure that was slightly higher in en-
ergy.
The energetics of small Cu clusters has been exten- Sachdev et al. 共1992兲 modeled Pt at larger sizes, by an
sively treated in a recent review by Alonso 共2000兲; here embedded atom potential and made simulated anneal-
we give a brief summary of the results for small sizes and ing calculations, finding that both at 13 and at 55 atoms
then focus on larger clusters. low-symmetry isomers are the lowest in energy. On the
Several ab initio calculations10 have been performed other hand, further global optimization results based on
for N 艋 10, again comparing a set of reasonably good semiempirical modeling 共Doye and Wales, 1998b; Bal-
structures. There is evidence of planar structures up to etto, Ferrando, et al., 2002; Massen et al., 2002; Sebetci
N = 5 or N = 6 maximum, as suggested by recent density- and Güvenc, 2003兲 gave preference to the icosahedral
functional calculations 共Jug, Zimmerman, Calaminici, et structure at N = 13. Doye and Wales 共1998b兲 and Massen
al., 2002兲. For N = 13, density-functional calculations et al. 共2002兲 found a low-symmetry structure at N = 55,
共Fujima and Yamaguchi, 1989兲 indicate that the icosahe- while Baletto, Ferrando, et al. 共2002兲 found the icosahe-
dron is favored over the cuboctahedron. dral structure also at this size, though with small cross-
For larger size, up to N ⬃ 100, global optimization over sizes among icosahedral, decahedral, and truncated
studies by semiempirical potentials have been per- octahedral structural motifs 共see Table I兲. Ab initio re-
formed. Doye and Wales 共1989b兲 used the Sutton and sults are even fewer. Yang et al. 共1997兲 found that at N
Chen 共1990兲 potential, while Darby et al. 共2002兲 used the = 13 several low-symmetry structures are lower in energy
Gupta 共1981兲 potential. In both cases, the best structure than the icosahedron and the cuboctahedron. Watari
at N = 13 is the icosahedron, in agreement with density- and Ohnishi 共1998兲 found that the cuboctahedron is
functional calculations, and there is no indication in fa- more stable than the icosahedron at N = 13 by density-
vor of disordered structures at geometric magic num- functional calculations. Recently, Fortunelli and Aprà
bers. Cu thus behaves like Ag, and very differently from 共2003兲 extended their calculations to N = 13, 38, and 55.
Au. Baletto, Ferrando, et al. 共2002兲 compared the ener- At N = 13, they found that the Ino decahedron is lower
gies of icosahedron, decahedron, and truncated octahe- in energy than the icosahedron and the cuboctahedron,
dron clusters at larger sizes, finding that the crossover
but a structure of D4h symmetry group originating from
from icosahedral to decahedral structures is around 1000
the symmetry breaking of the cuboctahedron is even
lower. At N = 55 the order of the structures is inverted,
10
See Bauschlicher 共1989兲, Bauschlicher et al. 共1988, 1989, and the icosahedron becomes lower than the Ino deca-
1990兲, Fujima and Yamaguchi 共1989兲, Massobrio et al. 共1995兲, hedron and the cuboctahedron. Fortunelli and Aprà
Jug, Zimmerman, Calaminici, et al. 共2002兲, Jug, Zimmerman, 共2003兲 attributed the results at N = 13 to the small size of
and Köster 共2002b兲. the molecule, while the behavior at N = 55 is intermedi-
ate between finite molecules and fully metallic systems. dron at N = 309, but not at N = 561. However, it must be
Very recent density-functional calculations by Aprà et al. kept in mind that the cuboctahedron and the Ino deca-
共2004兲 show that rosette structures, originating from the hedron are not usually favorable fcc and decahedron
disordering of one or two vertices in icosahedra of 55 clusters. This observation is in agreement with previous
atoms, are considerably lower in energy than the icosa- density-functional calculations by Jennison et al. 共1997兲,
hedron itself. This result would support the preference who showed that for N = 140, the truncated octahedron
of Pt for low-symmetry structures at icosahedral magic is favored over the icosahedron structure obtained by
numbers. removing seven vertex atom from the Ih147, while in Ag
the opposite happens.
e. Palladium clusters Global optimization studies up to N ⯝ 100 by the Sut-
ton and Chen 共1990兲 potential give for Pd the same re-
The energetics of small Pd clusters have been investi-
sults as for Ag, with icosahedron structure at N = 55, as
gated by several groups employing different methods.11
confirmed also in the optimization of the Gupta 共1981兲
Besides their catalytic properties, these clusters are very
potential by Massen et al. 共2002兲. At larger sizes, a com-
interesting because their lowest-lying isomers could
parison of the different structural motifs shows that Pd
have nonzero spin 共Reddy et al., 1993; Watari and
behaves in a similar way to Pt 关with rather small cross-
Ohnishi, 1998兲, being thus magnetic. Zhang et al. 共2003兲
over sizes 共see Table I兲, and fcc clusters already in close
have recently performed an extensive study of the sta-
competition with the other motifs at N ⬃ 100兴 when
bility of Pd clusters within the density-functional ap-
modeled by the Rosato et al. 共1989兲 potential, while it
proach at N 艋 13. In this size range they compared sev-
behaves very similarly to Ag when treated by means of
eral 1D, 2D, and 3D isomers; moreover, they considered
embedded atom potentials 共Baletto, Ferrando, et al.,
a few selected structures at N = 19 and 55. Their results 2002兲. Calculations by Jennison et al. 共1997兲 better sup-
indicate that the lowest-lying isomers are 3D starting port the results from the Rosato et al. 共1989兲 potential,
with the tetramer 共Zacarias et al., 1999; Moseler et al., finding that fcc structures are more favored in Pd than in
2001兲, and that icosahedral structures are favored over Ag. However, this point would need further investiga-
both decahedral and cuboctahedral structures for N tion, and it is not resolved by the analysis of the avail-
= 13 and 55. These results are in good agreement with able experimental data. José-Yacamán, Marín-Almazo,
previous calculations by Kumar and Kawazoe 共2002兲. and Ascencio 共2001兲 observed by transmission electron
On the other hand, Watari and Ohnishi 共1998兲 found microscopy the thiol-passivated Pd nanoparticles in the
that the cuboctahedron is more stable than the icosahe- range of 1 – 5 nm diameter, seeing a variety of structures,
dron at N = 13 according to density-functional calcula- ranging from fcc 共simple and twinned兲, to icosahedral, to
tions. Moseler et al. 共2001兲 were able to compare their decahedral, to amorphous structures. They were able to
results on vertical electron detachment energies for an- observe rather large icosahedral clusters, explaining
ionic clusters with the experimental data 共Ervin et al., their presence as being probably due to kinetic trapping
1988; Ho et al., 1991; Ganteför and Eberhardt, 1996兲, effects.
obtaining a good agreement.
At larger sizes, ab initio results are few, being re-
stricted to the comparison of a small set of selected f. Nickel clusters
structures at some special sizes. Kumar and Kawazoe As in the case of Cu, small Ni clusters have been re-
共2002兲 have compared icosahedron with cuboctahedron cently reviewed by Alonso 共2000兲. Reuse and Khanna
and Ino decahedron clusters at N = 55 and 147, finding 共1995兲 and Reuse et al. 共1995兲 performed several density-
that slightly distorted icosahedral structures are the low- functional studies of small Ni clusters, concluding that
est in energy in both cases. Nava et al. 共2003兲 also found the lowest-lying isomers are nonplanar for N 艌 4. At N
that a Jahn-Teller distorted icosahedron is lower in en- = 7, two isomers, the pentagonal bipyramid and the
ergy than a perfect icosahedron at N = 55. Moreover, capped octahedron, are in close competition 共Nayak et
Nava et al. 共2003兲 found that icosahedra and cuboctahe- al., 1996兲. The former is favored by density-functional
dra are very close in energy at both N = 147 and N 共Nygren et al., 1992兲 and embedded-atom 共Boyakata et
= 309, with the icosahedra prevailing at 147 and cuboc- al., 2001兲 calculations, while the latter is most likely to
tahedra at 309. By tight-binding calculations, Barreteau be observed in the experiments 共Parks et al., 1994兲, al-
et al. 共Barreteau, Desjonquères, and Spanjaard, 2000; though the experimental data do not completely rule out
Barrateau, Guirado-Lopez, et al., 2000兲 found that the the pentagonal bipyramid 共Nayak et al., 1996兲. Nayak et
icosahedron is still lower in energy than the cuboctahe- al. 共1996兲 performed ab initio calculations, finding that
these structures are almost degenerate in energy; then
11 they performed molecular-dynamics simulations by the
See Valerio and Toulhoat 共1996, 1997兲, Jennison et al.
Finnis and Sinclair 共1984兲 semiempirical potential, find-
共1997兲, Zacarias et al. 共1999兲, Barreteau, Desjonquères, and
Spanjaard 共2000兲, Barreteau, Guirado-López, et al. 共2000兲, ing that the capped octahedron has a wider catchment
Efremenko and Sheintuck 共2000兲, Guirado-López et al. 共2000兲, basin, becoming thus much more favorable at high tem-
Efremenko 共2001兲, Krüger et al. 共2001兲, Moseler et al. 共2001兲, peratures. This is clear evidence of an entropic effect
Roques et al. 共2001兲, Kumar and Kawazoe 共2002兲, Nava et al. 共see Sec. IV.A兲. At N = 13, Parks et al. 共1994兲 experimen-
共2003兲, Zhang et al. 共2003兲. tally identified the icosahedron as the most stable struc-
ture. Ab initio calculations at the same size 共Reuse and Soler et al. 共2000兲. What follows is a summary of these
Khanna, 1995; Reuse et al., 1995兲 have shown that the works. The energetic model is the Gupta 共1981兲 or
icosahedron is favored over the cuboctahedron, but the Rosato et al. 共1989兲 potential, which predicts the correct
most stable isomer is obtained by distorting the icosahe- surface reconstructions 共Guillopé and Legrand, 1989兲
dron slightly to obtain a cluster with D3d symmetry and reproduces quite accurately the diffusion barriers
group. The experimental observations 共Parks et al., 1995, 共Montalenti and Ferrando, 1999a, 1999b; Ala-Nissila et
1997, 1998兲 indicate a truncated octahedron structure at al., 2002兲 for these metals. In this framework, the poten-
N = 38, a capped decahedron structure at N = 39, and tial energy E of a cluster of N atoms is E = 兺i=1
N
Ei, where
共possibly defected兲 icosahedral structures at N = 55. The- the energy of atom i is given by
冑兺
oretical results are in reasonable agreement with these nv nv
experimental findings. Different global optimization re-
sults within semiempirical schemes 共Doye and Wales, Ei = A 兺
j=1
e−p共rij/r0−1兲 −
j=1
e−2q共rij/r0−1兲 , 共11兲
1998b; Grygorian and Springborg, 2003兲 and tight-
binding calculations 共Lathiotakis et al., 1996兲 predict fcc where nv is the number of atoms within an appropriate
and icosahedral structures at N = 38 and 55, respectively. cutoff distance 共in the following we include only the first
Moreover, capped decahedral structures just above size neighbors兲, and A , , p , q are parameters fitted to the
38 are found 共Wetzel and DePristo, 1996; Andriotis and bulk properties of the element. The first term in Eq. 共11兲
Menon, 2004兲. At larger sizes, the comparison of the is a repulsive Born-Mayer energy, while the second is
different structural motifs by different semiempirical ap- the attractive band energy. Following Tománek et al.
proaches 共Cleveland and Landman, 1991; Mottet et al., 共1985兲, one can eliminate the parameters A and , in
2004兲 shows that the crossovers icosahedral→decahedral order to have a function of 共p , q兲 and of the cohesive
and decahedral→ fcc take place at large sizes as in the energy per atom Ecoh. This is achieved by requiring that
case of Cu 共see Table I兲. in the bulk crystal at equilibrium Ei = Ecoh and Ei / r
= 0 for r = r0. The result is
4. General structural properties of noble-metal and
quasi-noble-metal clusters Ei =
兩Ecoh兩 v
冋兺 n
q e−p共rij/r0−1兲
12共p − q兲 j=1
册
Here we sketch general trends among the six metals
of the previous section with respect to three features:
formation of planar clusters, magnitude of crossover
sizes among the motifs, and preference for low-
− 冑12p 冑兺 nv
j=1
e−2q共rij/r0−1兲 . 共12兲
symmetry global minima at geometric magic sizes. This explicitly shows that the properties of the potential
Concerning the preference for formation of planar depend only on the parameters 共p , q兲, Ecoh and r0 play-
structures, there is a clear indication of an increasing ing the role of scale factors on energy and distance.
tendency going down from the 3d to the 5d series and Since atomic distances rij in noncrystalline structures are
from left to right in the Periodic Table. Thus Au has the not optimal, one can expect a metal that strongly in-
strongest tendency, followed by Ag, Pd, and Pt, all three
creases its energy for a change in rij 共i.e., that has a sticky
being at the same level 共however, there is still some de-
interatomic potential兲 to have small crossover sizes
bate about planar Pt clusters兲; Cu and Ni have no pref-
共Doye et al., 1995兲. In a solid at equilibrium, all 12 first
erence at all for planar structures. Several groups have
neighbors are at rij = r0. When one changes all rij by a
investigated the origin of this trend. Bravo-Pérez et al.
common factor rij → 共1 + 兲rij, developing the crystal en-
共1999b兲 correlated the preference for planar structures
ergy per atom Ei共兲 in Eq. 共12兲 共with nv = 12兲 to the sec-
in Au to the fact that nonadditive many-body interac-
tions are stronger than additive two-body ones in this ond order and dividing it by the equilibrium value 兩Ecoh兩,
element. Bonacić-Koutecký et al. 共2002兲 noticed that in one obtains 共Baletto, Ferrando, et al., 2002兲
planar Au clusters, d electrons contribute more to the Ei共兲 − Ei共0兲 1 2
bonding than in 3D structures; this would also qualita- 共兲 = = pq. 共13兲
兩Ei共0兲兩 2
tively explain the weaker tendency to planar clusters for
Ag, because in Ag the bonding is more of s type. Finally, Here 1 = 共兲 / 2 = pq / 2 is essentially the product of the
Häkkinen et al. 共2002兲 investigated Au7−, Ag7−, and Cu7− bulk modulus and the atomic volume divided by the co-
by density-functional calculations and demonstrated that hesive energy per atom of the bulk crystal. Thus the
the propensity of Au clusters to favor planar structures larger the pq, the smaller the crossover sizes from icosa-
is correlated with the strong hybridization of the atomic hedra to decahedra NIh→Dh and from decahedra to fcc
5d and 6s orbitals due to relativistic effects. crystallites NDh→fcc, as can be seen in Table I.
The tendency to form strained structures like icosahe- Let us now discuss the tendency to form low-
dra and decahedra, leading to large crossover sizes, and symmetry structures at geometric magic sizes 共referred
the tendency to present low-symmetry structures at geo- to as the tendency to amorphization in the following兲.
metric magic numbers have been discussed, in the This tendency is due to a specific feature of the metallic
framework of the same well-defined and quite reliable bonding, which derives from its many-body character
energetic model, by Baletto, Ferrando, et al. 共2002兲 and and relates the optimal distance of the bonding to the
coordination of the atom 共bond-order/bond-length cor- difference being the indication that Pt should have a
relation兲. This can be easily seen by taking a number of stronger amorphization tendency than Pd, due essen-
neighbors 1 艋 nv 艋 12 in Eq. 共12兲, all at the same distance tially to the comparatively weaker enthalpy of melting
r. Minimization with respect to r leads to the optimum of Pt 共the ratio ⌬Hmelt / 兩Ecoh兩 is much smaller in Pt than
distance r*共nv兲, in Pd兲.
冉 冊
Finally, let us compare metals with Lennard-Jones
r*共nv兲 1 nv clusters, in order to sketch a qualitative picture of the
=1+ ln , 共14兲
r0 2共p − q兲 12 effects of many-body forces. If one applies the criterion
of Eq. 共13兲 to Lennard-Jones clusters, one finds a value
which is more and more contracted for decreasing nv. It
also leads to the energy of 1, which is even larger than those for Au, Pt, and Pd.
冉 冊
This would suggest that Lennard-Jones systems have a
共p−2q兲/2共p−q兲
nv weaker tendency to form icosahedral clusters than these
E*共nv兲 = − 兩Ecoh兩 . 共15兲 metals, but this is not the case, since crossover sizes
12
icosahedron→ decahedron and icosahedron→ fcc are
The atoms on the surface of the cluster try to contract in much larger for Lennard-Jones clusters than for Au, Pt,
order to minimize their elastic energy 共Soler et al., 2001兲. or Pd. This happens because the bond-order/bond-
In the case of highly coordinated structures like the length correlation of metallic elements tends to destabi-
icosahedra 共which have intrashell expanded distances兲, lize icosahedral structures. In fact, metals would prefer
the optimization of the bond lengths is made at the ex- contracted interatomic distances for the low-
pense of the number of bonds. Therefore one expects coordination surface atoms, and bulk distances for the
amorphization to be easy in the elements with high elas- highly coordinated inner atoms. This is exactly the op-
tic energy 共i.e., large pq兲 and strong contraction of the posite of what happens in perfect icosahedral structures,
bonds with decreasing coordination, the latter leading to which have contracted internal distances and expanded
a weak dependence of E* on nv. The contraction of the surface distances. Moreover, in some metals such as Pt,
bonds and the dependence of E* on the coordination bond directionality effects 共which are not included in the
can be quantified by the following dimensionless param- potentials considered in Table I兲 can be important 共For-
eters: tunelli and Velasco, 2004兲 and favor the appearance of
nv dr* 1 共111兲-like hexagonal facets on the cluster surface 共Aprà
2 = = , et al., 2004兲, with a further destabilizing effect on icosa-
r0 dnv 2共p − q兲 hedral clusters.
nv dE* p − 2q
3 = * = . 共16兲 5. Silicon clusters
E dnv 2共p − q兲
Silicon nanoclusters are of great practical interest be-
As is evident from Table I, all parameters agree in indi- cause of their intense photoluminescence at room tem-
cating that Au has by far the strongest tendency to perature and the presence of quantum size effects.
amorphization, having the largest 1 and 2 and the There is an ongoing debate about the size at which the
smallest 3, followed by Pt and Pd; Ag and especially Cu most favorable clusters adopt the bulklike diamond
and Ni have the weakest tendency. structure. Bachels and Schäfer 共2000兲 produced neutral
On the same line of reasoning, Soler et al. 共2000兲 de- Si clusters in a laser vaporization source and measured
fined a parameter based solely on experimental quanti- their binding energy in samples having average sizes N̄
ties to extend the estimate of the tendency to amor- from 65 up to 890 atoms. They showed that the binding
phization to other systems. This parameter is A and is energy per atom Eb in this size range scales as N1/3, this
defined as the elastic energy ␦Eel that is needed to form being characteristic of approximately spherical clusters
an ordered surface with contracted atomic distances, di- 共Kaxiras and Jackson, 1993a兲. At smaller sizes, different
vided by the amorphization energy ␦Eam which is re- regimes in the behavior of Eb with N were found, as can
quired to form a scattered distribution of bond lengths. be seen from Fig. 15. There, Bachels and Schäfer 共2000兲
␦Eel is expressed by means of the 共Voigt-averaged兲 bulk plotted, besides their results at large sizes, Eb for smaller
and shear moduli B and G. ⌬Eam is approximated by the clusters 共N 艋 7兲 obtained from the results of other
enthalpy of melting ⌬Hmelt, which is an estimate of the groups 共Jarrold and Honea, 1991; Schmude et al., 1993,
energetic cost to form amorphous structures resembling 1995; Fuke et al., 1994兲. Three regimes are clearly
those found in liquids. This leads to shown. For N ⬍ 10 the binding energy increases rapidly
␦Eel v共3B − 5G兲2 with the cluster sizes, and compact elementary units are
A = ⯝ , 共17兲 built up. For 10⬍ N ⬍ 25, Eb is practically independent
⌬Eam 320B⌬Hmelt
of N, as would happen for prolate structures 共Kaxiras
where v is the atomic volume. Equation 共17兲 is valid for and Jackson, 1993a兲. This agrees with the previous ob-
small clusters having almost all atoms on their surface. servation of small prolate Si clusters by Jarrold and Con-
Elements with large A are expected to have a stronger stant 共1991兲. Finally, for larger clusters the N1/3 behavior
tendency to amorphization. As can be seen in Table I, is recovered. Bachels and Schäfer 共2000兲 were also able
the inspection of A confirms the above trends, the only to produce metastable prolate structures at sizes up to
brecht et al., 1997; Ehbrecht and Huisken, 1999; Ledoux isomers are found at N = 38 共truncated octahedron兲, N
et al., 2000兲. This would indicate that the transition to = 75 关共2,2,2兲 Marks decahedron兴 and 101 关共2,3,2兲 Marks
crystalline structures is around N = 400 atoms, as Yu et al. decahedron兴, and that N = 55 is not a magic number. At
共2002兲 found by simulated annealing tight-binding calcu- that size, the icosahedron is higher in energy than the
lations. best decahedron structure by 0.3 and 2 eV according to
the Pacheco and Prates-Ramalho 共1997兲 and Girifalco
6. Clusters of fullerene molecules 共1992兲 potentials, respectively.
These results completely disagree with the experimen-
The condensed-phase properties of C60 molecules tally observed structures. In fact, Martin et al. 共1993兲 and
have been the subject of considerable interest because Branz et al. 共2000, 2002兲 found that clusters grown at low
of the unusual character of molecular interactions. In T and annealed at ⬃500 K 共to allow the less bound sur-
fact, above room temperature, C60 molecules can be face molecules to evaporate兲 present a mass spectrum
considered as large spherical pseudoatoms which are with a clear sequence of icosahedral magic numbers up
free to rotate; the effective interaction between these to very large sizes, well above N = 100 共see Fig. 17兲. The
pseudoatoms is extremely short-ranged relative to the peak at N = 55 is very evident, and no peaks are found at
large equilibrium pair separation. This is at the origin of N = 38 and 75. The mass spectra are qualitatively similar
peculiar properties. In fact, such sticky interactions 共see for neutral, positively and negatively charged clusters
Fig. 7兲 disfavor all strained configurations, like those oc- 共Branz et al., 2002兲. Recently, Rey et al. 共2004兲 compared
curring in icosahedra or in the liquid phase. Indeed, the the neutral and singly-ionized cluster structures in a
existence of a liquid phase for bulk C60 共Hagen et al., model including the Girifalco 共1992兲 potential plus a
1993; Caccamo et al., 1997; Ferreira et al., 2000兲 is still point polarizable dipole electrostatic model. They found
debated. Therefore clusters of C60 molecules are on the that the structures of ionized clusters are very similar to
opposite side with respect to clusters of alkali metals, those of neutral clusters, thus confirming the observa-
and we expect noncrystalline structures to be the global tions. Branz et al. 共2002兲 found decahedra and close-
minima only for aggregates of a small number N of mol- packed structures only after further annealing at higher
ecules. T. This result indicates the possible existence of kinetic
This qualitative prediction has been confirmed by all trapping effects in the formation of the clusters of C60
existing calculations. We can divide these studies into molecules 共Baletto, Doye, and Ferrando, 2002兲, as we
two classes. The first uses an all-atom potential, with discuss in Sec. V.B.5. Trapping effects are overcome only
each carbon atom interacting with atoms of other mol- after a strong annealing.
ecules by a Lennard-Jones potential. This approach in- The resulting high-T experimental structures, how-
cludes deviations from spherical symmetry, but at ever, still do not coincide with those predicted by the
present allows global optimization only for small N. The Girifalco 共1992兲 and Pacheco and Prates-Ramalho
second class uses spherically averaged potentials, such as 共1997兲 potentials. In fact, there is a sequence of experi-
the Girifalco 共1992兲 potential, in which Lennard-Jones mental magic numbers that can be attributed to the
centers are continuously and uniformly distributed on Leary tetrahedron at N = 98 and to its fragments down to
the surface of a sphere, or the potential developed by N = 48, while the calculations do not attribute special sta-
Pacheco and Prates-Ramalho 共1997兲, which is derived by bility to these structures. This discrepancy is probably
fitting density-functional calculations. The Girifalco due to the fact that even the Pacheco and Prates-
共1992兲 potential is purely two-body, whereas the Pacheco Ramalho 共1997兲 potential is too sticky; a slightly less
and Prates-Ramalho 共1997兲 potential includes two-body sticky Morse potential gives the Leary tetrahedron as a
and three-body terms 共the latter, however, being of magic structure 共Doye et al., 2001兲.
rather small importance兲.
All these approaches agree in predicting that icosahe-
dral structures are favored only at very small N. All-
atom potentials favor icosahedral structures up to N IV. THERMODYNAMICS OF FREE NANOCLUSTERS
= 16 共Doye et al., 1997; Garcia-Rodeja et al., 1997; Rey et
al., 1997兲, while calculations with the Girifalco 共1992兲 In this section, we analyze the effects of raising the
potential, which is the stickiest, indicate that icosahedra temperature on cluster structures. These effects may in-
are the lowest in energy only up to N = 13 共Rey et al., clude solid-solid structural transitions and the melting of
1994; Wales, 1994a; Doye and Wales, 1996b兲. Finally, the the cluster if the temperature is raised enough. Both
Pacheco and Prates-Ramalho 共1997兲 potential favors solid-solid transitions and melting are cases that show
icosahedral structures up to N = 15. Larger clusters are the peculiar thermodynamic behavior of small finite sys-
either based on decahedra or on close-packed struc- tems such as clusters. Indeed, the thermodynamics of
tures, as shown by Doye et al. 共2001兲, who performed an finite systems is a fascinating and complex field, involv-
exhaustive basin-hopping global optimization study up ing many subtleties. Here we have no intention of being
to N = 105 on the basis of both Pacheco and Prates- exhaustive and refer readers who need more complete
Ramalho 共1997兲 and Girifalco 共1992兲 potentials. Close- treatments to existing monographs, from the classical
packed structures become more frequent as the size in- book of Hill 共1964兲 to the excellent book by Wales
creases. Both potentials indicate that the most stable 共2003兲. In the following we treat only those issues that
where
Zs = ZstrZsrotZsvib ,
Zstr and Zsrot
are related to the center-of-mass
translation and to rigid rotational motions, respectively,
共20兲
Zstr = 冉
V
MkBT
2ប2
冊 3/2
, Zsrot = 冉 2kBTĪs
ប2
冊 3/2
, 共23兲
冉 冊
k BT be evaluated by the superposition approximation 共Doye
兿
0
= e −Es . 共22兲 and Wales, 1995兲. Within this approximation, Z is ob-
i=i បs,i
tained by summing up the contributions from all signifi-
The classical expressions for Zstr and Zsrot are cant minima. This gives
FIG. 19. 共Color in online edition兲 Schematic representation of FIG. 20. Structural phase diagram in the N,T plane for
the probabilities pS and pS⬘ of the local energy minima S and Lennard-Jones clusters in the harmonic superposition approxi-
S⬘, with S⬘ having higher energy than S vs temperature. In the mation. From Doye and Calvo, 2002.
temperature range close to the transition temperature TSS⬘ the
shift upwards through icosahedral→ decahedral and
two structures coexist, being almost equally likely.
decahedral→ fcc crossover sizes with increasing tem-
perature, as can be seen in the 共coarse-grained兲 struc-
0 tural phase diagram of Fig. 20. This happens because
n sZ s n sZ s nsĪs3/2e−Es ⍀s− icosahedral structures have on average smaller vibra-
ps = ⯝ Mmin ⯝ Mmin , 共24兲
Z tional frequencies than decahedral ones, the latter hav-
兺 兺
0
n Z 3/2 −E
nĪ e ⍀− ing softer vibrations than fcc clusters 共Doye and Calvo,
=1 =1
2002兲. Metals modeled by Sutton and Chen 共1990兲 po-
where ⍀s = 共⌸i i,s兲1/ is the geometric average of the vi- tentials behave in a qualitatively similar way 共Doye and
brational frequencies of s. Calvo, 2001兲. A discussion of the observation of solid-
Let us now consider the simplest case of a potential- solid transitions in experiments and simulations on spe-
energy surface having two minima, s and s⬘ 共with Es0 cific systems is given in Sec. IV.C. Here we only remark
that solid-solid transitions may be extremely slow in
⬍ Es0 兲, and calculate the ratio ps / ps⬘ between their occu-
⬘ typical situations, so that observing them may require a
pation probabilities as a function of T. Assuming that
substantial overheating of the initial structure 共Koga et
Īs ⯝ Īs⬘, one obtains al., 2004兲, to surmount the energy barriers leading to
ps
=
Z sn s
p s⬘ Z s⬘n s⬘
= e−⌬E
0
冋 冉 冊册
n s ⍀ s⬘
n s⬘ ⍀ s
, 共25兲
escape from the initial basin.
2. Anharmonic and quantum corrections
The harmonic superposition approximation is often
where ⌬E0 = Es0 − Es0 . Since ⌬E0 ⬎ 0 we have two cases:
⬘ accurate for cluster thermodynamics up to temperatures
共i兲 if ns / ⍀s ⬎ ns⬘ / ⍀s⬘, s is favored over s⬘ for all tem- close to the melting range, as shown for Ag38 and Cu38
peratures; by Baletto et al. 共2004兲. However, there are cases in
which this approximation is not sufficient, and anhar-
共ii兲 if ns / ⍀s ⬍ ns⬘ / ⍀s⬘, for T ⬎ Tss, s⬘ becomes more monic effects must be included 共Doye and Wales, 1995兲.
favored than s and thus a solid-solid transition is Solid-solid transitions can be close to the melting tem-
possible; see Fig. 19. perature, in which case anharmonic effects are not neg-
From the above equations, we estimate Tss as ligible. Moreover, the harmonic approximation may
strongly overestimate the probability of minima that
⌬E0 have low-barrier escape paths. An example of failure of
Tss = . 共26兲 the harmonic approximation is found by Wang, Blastein-
kB关ln共ns⬘/ns兲 + ln共⍀s/⍀s⬘兲兴
Barojas, et al. 共2001兲 and Doye and Calvo 共2003兲.
To find a solid-solid transition, not only must case 共ii兲 One can introduce anharmonic effects via
hold, but Tss must be below the melting range of the T-dependent frequencies, i.e., ⍀̃s共T兲 = ⍀s共1 − s0 / 兲,
cluster. where 0 is a measure of the anharmonicity. This then
How do entropic contributions behave in typical gives for the transition temperature, neglecting the per-
cases? Doye and Calvo 共2002兲 throughly analyzed mutational contribution,
冋 冉 冊册
Lennard-Jones clusters within the harmonic superposi-
tion approximation. They grouped together the minima  − s0
ss
anHA
= ln共⍀ /⍀ s⬘ 兲 + ln , 共27兲
pertaining to each motif 共icosahedron, decahedron, and ⌬E0
s
 − s0⬘
fcc兲, thus being able to estimate transition temperatures
between structural motifs and not simply between pairs where the second term represents the first order ap-
of minima. They found that the entropic contributions proximation to the anharmonic correction to ss anHA
anHA
= 1 / kBTss . To apply the previous equation it is neces- 共1998兲. However, there are several differences between
sary to estimate 0 but the available methods do not the solid-liquid transition of clusters and that of its bulk
allow one to treat large sizes. counterpart:
Quantum corrections can be inserted both in Zsrot and 共i兲 The melting point is reduced 共with a few known
Zsvib. Since quantum corrections to Zsrot should become exceptions兲 with a complex dependence on size.
important only at very low temperatures, we now con-
共ii兲 The latent heat is smaller; this can be understood,
sider only the corrections to Zsvib. These corrections are
for example, by noting that disordering the sur-
very easily introduced within the harmonic approxima-
face costs less than disordering inner atoms.
tion. The quantum partition function of a set of oscilla-
tors is given by 共iii兲 The transition does not take place sharply at one
definite temperature, but smoothly over a finite
temperature range. There, solid and liquid phases
兿
0
Zsvib = e−Es 关2 sinh共បi,s/2兲兴−1 . 共28兲 may coexist dynamically in time 共Berry et al.,
i=1 1988; Lynden-Bell and Wales, 1994兲. When one
observes the cluster over a long time interval,
The classical limit is valid when it is possible to approxi-
there will be subintervals in which the cluster ap-
mate the sinh共បi,s / 2兲 with its argument; thus it is valid
pears to be solid and others in which the cluster is
for high temperatures. The introduction of quantum os-
fully liquid.
cillators modifies the expression of the ratio between the
occupation probabilities of two minima s and s⬘ in the 共iv兲 The heat capacity can become negative in micro-
following way: canonical environments 共Schmidt et al., 2001兲.
This means that the microcanonical average ki-
冤 冥
netic energy may be a nonmonotonically increas-
ps ns
兿i sinh共បi,s⬘/2兲 ing function of the total energy in the range of the
= e−⌬E
0
. 共29兲 transition 共Bixon and Jortner, 1989兲.
p s⬘ n s⬘
共v兲
兿i sinh共បi,s/2兲 The melting transition depends on cluster struc-
ture and chemical ordering 共this being, indeed, a
nonequilibrium effect兲.
In particular, we note that here the temperature depen- Often the melting transition is preceded by premelting
dence is also in the vibrational contribution and not only phenomena. To quote Calvo and Spiegelman 共2000兲,
in the Boltzmann factor. To understand when quantum “premelting phenomena are characteristic of isomeriza-
corrections are needed we may refer to the Debye tem- tions taking place in a limited part of the configuration
perature ⌰D. If the temperature of the system is above space,” for example, isomerizations involving surface at-
0.70⌰D the system can be treated as classical to a good oms only 共in this case the term surface melting is used兲.
approximation, while at lower temperature we also need Premelting phenomena are often singled out by addi-
to take quantum effects into account 共Ashcroft and Mer- tional peaks in the specific heat vs temperature.
min, 1976兲. Calvo et al. 共2003兲 satisfactorily explained the
finite-temperature spectroscopic properties of CaArN
clusters including quantum and anharmonic corrections 1. Experimental methods
in their calculations.
Following Haberland 共2002兲, experiments studying
cluster melting can be divided into two classes:
B. Melting of nanoclusters 共i兲 study of the change of some physical property
across the melting point 共for example, changes in
The concepts of solid and liquid states, which are photon or x-ray diffraction patterns兲
commonly employed when discussing extended systems,
共ii兲 measurement of the caloric curve E = E共T兲, that is,
can be applied to clusters. In fact, at low temperature,
the particles of a cluster spend most of the time making the cluster’s internal energy E as a function of T.
small-amplitude vibrations around the global minimum, Takagi 共1954兲 made the first observation of the melt-
in analogy to what happens in bulk solids. If the tem- ing point depression by transmission electron micros-
perature is increased, other minima begin to be popu- copy. This is a standard technique for studying the size-
lated, and this is associated with the onset of some dif- dependent melting point of small particles by
fusive motion. Finally, if the temperature becomes high monitoring the changes in the diffraction pattern associ-
enough, the cluster explores the basins of a huge num- ated with the disordering of the structure. Electron and
ber of minima, with fast rearrangements, thus behaving x-ray diffraction and nanocalorimetry techniques have
like a liquid droplet. Within this description, cluster been used to study melting in deposited clusters 共Lai et
melting is seen as an isomerization transition, with the al., 1996; Peters et al., 1998; Efremov et al., 2000兲. At
number of probable isomers increasing drastically after present these methods are, however, not applicable to
some threshold temperature. A nice example of this be- free, mass-selected clusters in vacuum for two reasons:
havior for Ag6 clusters is given by Garzón, Kaplan, et al. first, no method of temperature measurement is known
14
In the common-neighbor analysis a signature is assigned to
each pair of neighbors. This signature is a triplet of integers
共r , s , t兲, where r is the number of common nearest neighbors of
two atoms of the pair, s is the number of nearest-neighbor
bonds among the r common neighbors, and t is the length of
the longest chain that can be formed with the s bonds. We have
found that the monitoring of the signatures 共r , s , t兲 = 共5 , 5 , 5兲,
共4,2,1兲, 共4,2,2兲 is sufficient to distinguish icosohedral, decahe-
dral, and fcc structures over a wide range of sizes 共Baletto,
Mottet, and Ferrando, 2001a; Baletto, 2003兲 during growth
simulations. The 共5,5,5兲 signature indicates pairs located along
a 共locally兲 fivefold symmetry axis. The 共4,2,1兲 signature is asso-
FIG. 23. Heat capacity and bond-length fluctuations in the 57- ciated with pairs with fcc neighborhood. The 共4,2,2兲 signature
atom Lennard-Jones cluster. Left panel, heat capacity curves. is associated with pairs comprising an atom of a 共locally兲 five-
Open circles and solid line represent the results of parallel fold axis and an atom outside the axis. In perfect fcc clusters
tempering simulations, while the dotted line and the thin solid one expects to find a large percentage of 共4,2,1兲 signatures and
line are the results of Metropolis Monte Carlo runs of different no 共5,5,5兲 and 共4,2,2兲 signatures. Comparing icosahedral and
length. Right panel, ⌬DF calculated in two Monte Carlo simu- decahedral clusters in the same size range, one finds that the
lations of different length 共the longer one corresponds to the percentage of 共5,5,5兲 signatures is much larger in icosahedra,
open circles兲. The temperature at which ⌬DF starts its strong while the percentage of 共4,2,1兲 signatures is larger in decahe-
increase corresponds well to the temperature of the heat ca- dra. Tables with the values of the percentages for these signa-
pacity peak. The heat-capacity c and ⌬DF are given in reduced tures are found in the dissertation of Baletto 共2003; see also
units 共see Frantz, 2001兲. Adapted from Frantz, 2001. Baletto, Mottet, and Ferrando, 2001a兲.
1 1
− sl共T − T0兲 + 共pl − p0兲 = − ss共T − T0兲 + 共ps − p0兲.
l s
共34兲
Here, one must distinguish between the pressure ps of a
solid cluster and the pressure pl of a liquid cluster. In
fact, the pressure inside a small object of radius r is
larger than the external pressure because of the Laplace
contribution pLap = 2␥ / r to the pressure, where ␥ is the
interface tension of the cluster and r is its radius. Since a
liquid and a solid cluster of N atoms can differ both in
interface tension 共␥lv for the liquid-vapor interface, ␥sv
for the solid-vapor interface兲 and in radius, they can
have different Laplace pressure terms,
FIG. 24. A particle with a solid core of radius r − ␦ and a liquid
2␥lv 2␥sv shell of thickness ␦.
pl = pext + , ps = pext + . 共35兲
rl rs
For a cluster of r ⬃ 10 nm, typical interface tensions are the case of metallic particles was given by Kofman et al.
of the order of 103 erg/ cm2, so that the Laplace pressure 共1994兲 and Vanfleet and Mochel 共1995兲; here we briefly
is much larger than pext under the usual conditions. Thus sketch their approach. The extension of this approach to
pext can be neglected in Eq. 共35兲. Moreover, for spherical molecular clusters 共by including van der Waals forces兲
clusters, can be found in Levi and Mazzarello 共2001兲.
冉冊
Let us consider a particle like that in Fig. 24, contain-
rs l 1/3
ing Nl particles in the liquid shell. Its free energy G is
= . 共36兲
rl s given by
Substituting Eqs. 共35兲 and 共36兲 into Eq. 共34兲, neglecting G = 共N − Nl兲s + Nll
冋冉 冊 册
pext, and taking into account that L = T0共sl − ss兲 is the la-
tent heat of melting per particle, one obtains r−␦ 2
+ 4r2 ␥sl + ␥lv + S⬘e−␦/ , 共39兲
1−
Tm共N兲
=
2
Tm共⬁兲 srsL
␥sv − ␥lv s
l
冋 冉冊册 2/3
. 共37兲
where
r
冋 册
r
C
Tm共N兲 = Tm共⬁兲 1 − , 共38兲 Here is the characteristic length of the interaction
N1/3
among atoms in liquid metals, and the term S⬘e␦/ takes
where C is a constant. This formula gives a very simple into account the effective interaction between the solid-
dependence for Tm共N兲 which can thus be considerably liquid and liquid-vapor interfaces. This effective interac-
lower than Tm共⬁兲 共Buffat and Borel, 1976; Lewis et al., tion is repulsive and favors the formation of a liquid
1997; Rytkönen, Valkealahti, and Manninen, 1998兲. An shell between the solid core and the vapor. For T not too
expression for C easily follows from Eq. 共37兲, but the far from Tm共⬁兲 one may approximate Nl共l − s兲
quantities involved in that expression may not be easy to ⯝ VlL关Tm共⬁兲 − T兴 / Tm共⬁兲, where Vl = 4关r3 − 共r − ␦兲3兴 / 3 is
evaluate. Moreover, several rather crude approxima- the volume of the liquid layer, and the density difference
tions are involved in Eq. 共37兲, so that usually C is con- between liquid and solid is neglected 共l = s = 兲. Mini-
sidered as a fitting parameter.
mizing G with respect to ␦, one finds the following solu-
Several attempts have been made to improve
tion for Tm共N兲:
Pawlow’s theory. Buffat and Borel 共1976兲 included
higher-order terms in Eq. 共32兲, and solved numerically
Tm共N兲 2␥sl S ⬘r 2
the resulting equation. Including higher-order terms is in 1− = 共1 − e−␦/兲 + e −␦/ .
principle more accurate, but these terms increase the Tm共⬁兲 L共r − ␦兲 L共r − ␦兲2
number of unknown parameters to be evaluated. Reiss 共41兲
and Wilson 共1948兲, Hanszen 共1960兲, and finally Sambles
共1971兲 refined Pawlow’s model by including the possibil- Pawlow’s result of Eq. 共37兲 is recovered in the limit
ity of surface melting, that is, of having clusters 共of total → 0, which means a sharp interface, or equivalently, no
radius r兲 made of an inner core of radius r − ␦ and an effective repulsive interaction between the solid-liquid
external liquid shell of thickness ␦. The melting tem- and the liquid-vapor interfaces. For molecular clusters,
perature is found by imposing the equilibrium condition this effective interaction is proportional to 1 / ␦2 instead
on this solid-core/liquid-shell particle. A derivation for of e−␦/ 共Levi and Mazzarello, 2001兲.
1−
Tm共N兲
=
2 ␥sl
再
Tm共⬁兲 lL r − ␦
+
␥lv
r
1−
s
l
冋 冉 冊 册冎 2/3
. 共42兲
al. 共2003兲 were able to measure the energy and the en-
tropy change in the melting of Na clusters. They found
that the peaks in Tm共N兲 are driven by the energy differ-
If ␥sl is evaluated as ␥sv − ␥lv 共that is, if the liquid shell ence between the liquid and the solid phases. The en-
perfectly wets the solid core兲, and ␦ = 0, Eq. 共42兲 reduces tropy difference is closely correlated to the energy dif-
to Eq. 共37兲. ference and simply causes a damping of the energetic
Both Eqs. 共41兲 and 共42兲 are more accurate than effects. This would show that the main indicator for a
Pawlow’s result down to small sizes 共see Fig. 25兲. Peters high Tm is the energetic separation of the global mini-
et al. 共1998兲 found that the solid-core/liquid-shell model mum from higher isomers. However, it is not yet clear
gives a better fit of the experimental melting tempera- whether entropic differences are always correlated to
tures of supported lead clusters. Chushak and Bartell energetic differences, or whether this is a trait of Na
共2001b兲 and Wang, Zhang, et al. 共2003兲 melted a series of clusters.
selected fcc clusters of gold and copper, respectively, by The irregular variations of the melting point in
molecular-dynamics simulations within an embedded- Lennard-Jones clusters were studied by Frantz 共2001兲,
atom energetic model. They found that Eq. 共38兲 is accu- who thoroughly analyzed the range 26艋 N 艋 60 by the
rate down to N ⬃ 103 and 5 ⫻ 102 for Au and Cu, respec- parallel tempering technique. Frantz 共2001兲 found that
tively. At smaller sizes, Eq. 共42兲 is in better agreement the peaks in Tm共N兲 were generally well correlated with
with the simulation data in the case of Au. Other simu- those of other stability indicators, such as the energetic
lation results are given by Ercolessi et al. 共1991兲, Lewis et separation of the second isomer from the global mini-
al. 共1997兲, and Qi et al. 共2001兲. Lai et al. 共1996兲 obtained mum ESM共N兲 − EGM共N兲, ⌬1共N兲, and ⌬2共N兲 关see Eq. 共6兲兴.
an excellent fit to their experimental data on the melting An exception was N = 58, a magic size for the stability
of tin clusters 共see Fig. 26兲 by the formula of Hanszen indicators, but not corresponding to a peak of Tm共N兲.
共1960兲; the same data were successfully refitted by means Finally, even though the melting point in nanoclusters
of Eq. 共41兲 共Bachels et al., 2000兲. is usually depressed, some evidence of exceptions to this
When the size dependence of the melting point is ex- rule is beginning to accumulate. The first experimental
amined on a fine scale, irregular variations are found, evidence of an exception is due to Shvartsburg and Jar-
especially at small sizes, where the addition or the re- rold 共2000兲, who studied the melting of Sn clusters. Small
moval of a single atom can have dramatic effects. There Sn clusters have a rather elongated structure, which
is a good agreement among several simulation results in should change to nearly spherical upon melting. No sig-
predicting that clusters of special stability, such as icosa- nature of this change was observed by Shvartsburg and
hedral clusters at magic sizes 共55, 147, etc.兲, melt at Jarrold 共2000兲, so they concluded that Sn cluster ions
higher temperatures than predicted by Eq. 共38兲 关see, for containing 10–30 atoms have a melting point at least
example, the cases of Lennard-Jones, Na, and noble- 50 K above the bulk one. This behavior has been con-
firmed by Joshi et al. 共2002兲, who performed ab initio the melting takes place, Rytkönen et al. calculated the
molecular-dynamics simulations of the melting of Sn10. radial distribution function, finding that, at nonmagic
They found that binding in such a small cluster is indeed icosahedral sizes, there is a clear tendency to surface
covalent, and that the specific heat of Sn10 shows a melting while the cores preserve an icosahedral mor-
shoulder around 500 K due to a permutational rear- phology.
rangement of atoms that preserves the trigonal prism Frantz 共1995, 2001兲 made a detailed systematic study
core of the ground state. Only at much higher tempera- of small Lennard-Jones clusters by Monte Carlo simula-
tures, T ⯝ 1500 K, does this core distort and break up, tions. He found that the smallest clusters presented an
yielding a peak in the specific heat around 2300 K. Joshi irregular dependence of their thermodynamic properties
et al. 共2003兲 also simulated the melting of Sn20, finding on size. For N ⬎ 25 some trends were pronounced. Icosa-
that it has a lower melting point than Sn10, but one that hedral packing was dominant 共with the exception of the
is still much higher than that of bulk Sn. Chuang et al. truncated octahedron at N = 38兲 and the heat capacity
共2004兲 have found by ab initio Langevin molecular dy- peak parameters formed two overlapping sequences as a
namics that Sn6, Sn7, and Sn13 also melt at a higher T function of N, depending on whether the overlayer had
than bulk Sn. Mackay or anti-Mackay stacking. In clusters with an
Small Sn clusters seem not to be the only ones to melt anti-Mackay overlayer, the heat-capacity peak shifted
at higher temperature than the bulk crystal. There is towards higher T and became smaller at increasing N,
recent experimental and theoretical evidence for gallium while clusters with Mackay rearrangements had small,
clusters 共Breaux et al., 2003; Chacko et al., 2004兲, whose low-T peaks that generally shifted to higher T and grew
high melting point is attributed to the fact that, in con- in size as N increased. There was a sequence of magic
trast to bulk Ga, binding in small clusters is fully cova- numbers, N = 36, 39, 43, 46, 49, 55, at which the heat-
lent. Finally, in their simulations, Akola and Manninen capacity peak was stronger. As already discussed in Sec.
共2001兲 observed a bulklike behavior of Al13− above the IV.B.3, this sequence correlates well with that extracted
Al bulk melting temperature. from the binding energy differences.
As a final remark, we note that thermodynamic effects
on structural stability and the melting of nanoclusters 2. Sodium clusters
suggest a more general definition of the stability, includ-
ing temperature effects 共Baletto, Rapallo, et al., 2004兲. Experiments by Martin et al. 共1994兲 and Schmidt et al.
共1998兲 have revealed a complex dependence of Tm共N兲
for Na clusters. Its irregular small-size behavior has al-
C. Studies of selected systems ready been discussed in Secs. IV.B.3. Liu et al. 共2002兲
performed a systematic simulation study of the melting
1. Lennard-Jones clusters
of different morphologies over a wide size range. They
There are several computational studies of melting in found that the melting points for all sizes and structural
Lennard-Jones clusters, especially at magic icosahedral types were in a narrow T range 共200– 300 K兲 and all
sizes. Early molecular-dynamics studies on the melting clusters presented a liquid-gas transition around 1000 K.
of Ar clusters by Briant and Burton 共1975兲 indicated a Another interesting point about the melting of Na
relatively sharp first-order-like transition at T below the clusters, which is of great general interest, is the pres-
bulk melting temperature. This result was later con- ence of premelting effects. A detailed study of this topic
firmed. At N = 55 and N = 147 all simulations indicate at 8 艋 N 艋 147 atoms has been performed by Calvo and
relatively sharp jumps in the caloric curves at T ⯝ 35 K Spiegelman 共2000兲 by a Monte Carlo thermodynamical
and T ⯝ 42 K, and the radial distributions confirm that analysis close to the solid-liquid transition, within a
whole clusters melted during the transitions 共Etters and semiempirical modeling by Gupta 共1981兲 potentials. Up
Kaelberer, 1975; Honeycutt and Andersen, 1987; Mat- to 147 atoms, the thermodynamics appears to be directly
suoka et al., 1992兲. At N = 13 the cluster fluctuates back related to the lowest-energy structures, and melting by
and forth between the two phases and a consistent de- steps is favored by the presence of surface defects. For
termination of Tm is very difficult. The breadth of the N ⬍ 75 the Tm presents a strong nonmonotonic behavior
solid-liquid transition is also revealed for Ar13 adsorbed with N, which is typical of geometric size effects. For
on a surface 共Blaisten-Barojas et al., 1987兲, where the larger sizes the transition becomes more and more simi-
cluster changes from an icosahedral, solidlike structure lar to the bulk case. Calvo and Spiegelman 共2000兲 find
at low T to a set of liquidlike structures at high T. Clus- evidence of premelting phenomena at small sizes, with
ters containing 309 or more atoms are observed to des- the caloric curves presenting multimodal behavior with
orb atoms at temperatures where the core is still solid increasing T. Simple isomerization between a few struc-
共Rytkönen et al., 1997兲. Thus it is very complicated to tures, surface melting, or competition between several
define their melting point, if the heating rate is slow. Fast funnels on the energy landscape may be the causes of
heating rates can, however, cause the superheating of this premelting. Premelting seems to be the rule for
the cluster. Rytkönen, Valkealahti, and Manninen 共1998兲 small Na clusters, the only exceptions being the very
found a rather good agreement with Eq. 共38兲, except stable magic icosahedral structures. The secondary
that Tm at small sizes and for icosahedral structures is peaks in the heat capacity become less pronounced at
higher than predicted analytically. To investigate how N ⬎ 100, indicating that premelting becomes less impor-
tant. Calculations by Gupta potentials and ab initio Li, Ji, et al. 共2000兲 made a thorough analysis at N
schemes 共Rytkönen, Häkkinen, and Manninen 1998, = 55 for Au, Ag, and Cu by means of molecular-
1999; Reyes-Nava et al., 2002兲 agree reasonably well dynamics simulations. Ag55 and Cu55 showed abrupt
with the experiments, but several aspects of the melting changes during the meltinglike transitions, while the
behavior of Na clusters are still to be understood. Calvo transition of Au55 seemed to proceed for a relatively
and Spiegelman 共2004兲 have recently reexamined the broader interval, with ⌬DF increasing gently from 300 up
melting behavior of Gupta Na clusters in the size range to 600 K and with a small, ladderlike energy jump in the
around 130 atoms, finding that the potential is somewhat caloric curve. The degrees of reduction for Tm were dif-
inadequate because it predicts strong premelting effects ferent among the three metals. Compared to Ag and Cu,
that are not observed in the experiments. These pre- Au exhibited the largest size-induced drop of Tm. This
melting effects are related to the surface melting of the
confirms the trends of Table I, since Cu also gives the
outer icosahedral shell.
most stable icosahedron cluster from the thermody-
namic point of view.
At N = 38 a complex melting behavior for Cu was
3. Noble-metal and transition-metal clusters found by Baletto et al. 共2004兲, using molecular-dynamics
simulations. A solid-solid transition took place from the
In the case of metallic clusters, the literature is exten- truncated octahedron at the global minimum. Then the
sive, especially for Au clusters.16 To begin, we remark cluster rearranged itself into defected decahedron struc-
that, although the melting point is depressed, its reduc- tures before melting, in analogy with the behavior of the
tion is smaller than that of Lennard-Jones clusters, and Lennard-Jones cluster of the same size 共Doye et al.,
it is strongly material dependent 共Jellinek et al., 1986; 1998兲. On the other hand, Ag38, which has the same
Garzón and Jellinek, 1991; Jellinek and Garzón, 1991兲. global-minimum structure as Cu38, does not exhibit any
Usually melting is accompanied by a peak in the specific solid-solid transition to defected decahedral structures.
heat, and by a substantial rearrangement of the cluster. At this size Au presents a coexistence phase region
But there are exceptions. For example, the simulations among different isomers already at T ⬃ 250 K 共Garzón et
by Westergren et al. 共2003兲 revealed that Pd34 melts with- al., 1999兲.
out an accompanying peak in the heat capacity, and the Molecular-dynamics simulations of the melting transi-
atoms become mobile without any significant change in tions for crystalline nickel clusters above N ⬃ 750 show
geometric structure. García-Rodeja et al. 共1994兲 and Lee
that Tm共N兲 closely follows Eq. 共38兲 共Qi et al., 2001兲,
et al. 共2001兲 studied several transition and noble metals,
while, for N ⬍ 500, icosahedral structures present higher
at very small sizes, around 13 atoms, modeled by Gupta
Tm and large latent heat. Similar results are found also
potentials. Their simulation results were in agreement
with those obtained by Güvenc and Jellinek 共1992兲. The for Cu 共Wang, Zhang, et al., 2003兲. For smaller N, the
salient result is that the behavior of Ni, Cu, Pd, Ag, and icosahedral packing is more stable and presents higher
melting points than those derived from Eq. 共38兲
Pt is similar, the main difference being that Pd13 presents
a more complex anharmonic behavior than Ag 共Wester- 共Valkealahti and Manninen, 1993兲.
gren and Nordholm, 2003兲. The 13-atom clusters un- Gold clusters have been studied intensively in recent
dergo a structural transition from a rigid, solidlike icosa- years 共see Cleveland et al., 1998, 1999; Lee et al., 2001; Li
hedral structure to a nonrigid, liquidlike one via an et al., 2002兲. All these studies agree that a solid-solid
intermediate temperature range in which both forms co- structural transformation from the low-T optimal struc-
exist. The caloric curves do not present any sharp tran- tures to icosahedral structures takes place below the
sition, and Tm is found by monitoring ⌬DF 关Eq. 共30兲兴 and melting temperature. Detailed analysis of the atomic
looking for a maximum in the specific heat. The instabil- trajectories and of the structural evolution indicates that
ity of some specific atom can play a key role in melting, this solid-to-solid transition is essentially without diffu-
as in the case of the capped atoms at N = 14. The atom sive motion, occurring quickly and involving many
added to the 13-atom icosahedron can diffuse rapidly at 共small兲 cooperative displacements of the atoms. The
T below the melting region, and this causes a small peak structural transformation is driven by the vibrational
in the specific heat 共García-Rodeja et al., 1994; Lee et al., and configurational entropy at elevated T 共Luo et al.,
2001兲 so that Tm is smaller than for the 13-atom cluster. 1987; Ajayan and Marks, 1988兲. A thorough molecular-
Similar behavior is found at N = 20 for the capped dynamics simulation study was made by Liu et al. 共2001兲.
double icosahedron. In contrast, when the double icosa- Different morphologies were compared up to N
hedron is not the global minimum, the heat capacity has ⬃ 25 000. At intermediate sizes, for all type of mor-
an unexpected behavior. For example, Pd19 shows a dis- phologies, Liu et al. 共2001兲 found that the melting pro-
tinct abrupt change at T ⬃ 400 K and a rounded-off cess occurs in three stages: a relatively long time of sur-
broad peak at higher T 共Lee et al., 2001兲. face disordering and reordering, a relatively short time
of surface melting, and finally a rapid overall melting.
Concerning the differences among the structural motifs,
16
See Buffat and Borel 共1976兲, Garzón and Jellinek 共1993兲, starlike decahedra are the hardest to melt, while icosa-
Cleveland et al. 共1997, 1998, 1999兲, Li, Ji, et al. 共2000; Li, Lee, et hedron clusters are the easiest, with regular decahedra
al., 2002兲, Lee et al. 共2001兲, and Koga et al. 共2004兲. being in between. Small cuboctahedra, up to N = 309 at
least, transform into icosahedra before melting, while cluster melts at temperatures comparable with other
large ones do not. Contrary to the other motifs, Tm of nearly spherical structures.
icosahedra saturates at N ⬎ 12 000. Liu et al. 共2001兲 also
compared different structures at identical sizes, finding
V. KINETIC EFFECTS IN THE FORMATION OF
that transition temperatures could differ by as much as NANOCLUSTERS
75 K. This nonequilibrium effect indicates the differ-
ences in kinetic stability of the different structures From the results reported in the previous sections,
against heating. one can see that there are discrepancies between the
Very recently Koga et al. 共2004兲 were able to heat up results of energetic and/or thermodynamic calculations
metastable gold icosahedra produced in an inert-gas ag- and the real outcomes of the experiments, viz., the struc-
gregation source 共see Sec. V.B.3兲. Upon heating to T tures that are actually observed in the production of free
= 1273 K, which is only 64 K below the bulk melting solid clusters. In some cases, the disagreement is of such
temperature of Au, they were able to produce a clearly a qualitative nature that it is unlikely to be due to the
dominant fraction of decahedron structures in the range failure of the energetic or of the thermodynamic model-
6 – 12 nm diameter. A considerable fraction of fcc clus- ing. To cite just the most striking cases, we mention the
ters was obtained only heating above the bulk melting observation of small decahedra and large icosahedra in
temperature, and only for diameters above 10 nm. Since the inert-gas aggregation experiments on the production
all calculated crossover sizes decahedron→ fcc at 0 K of Ag clusters 共Reinhard, Hall, Ugarte, and Monot,
are much smaller 共Cleveland et al., 1997; Baletto, Fer- 1997兲, the production of large icosahedral clusters of C60
rando, et al., 2002兲, these experimental results give sup- molecules 共Martin et al., 1993; Branz et al., 2000, 2002兲,
port to the hypothesis of an upward displacement of the and the detection of octahedral Al clusters presenting
crossover size with increasing temperature, in agreement only 共111兲 facets 共Martin et al., 1992兲. Moreover, there is
with the predictions of the harmonic theory 共Doye and still quantitative disagreement between the theoretical
Calvo, 2001兲, as can be seen in Fig. 20. estimates 共based on the total energy optimization兲 and
the experimental data about the crossover sizes for Ar
4. Silicon clusters
clusters 共Ikeshoji et al., 2001兲. These results indicate that
kinetic effects must be taken into account to explain the
Wang, Wang, et al. 共2001兲 performed a systematic actual free-cluster formation in the experiments. As dis-
simulation study of structural transitions and thermody- cussed in Sec. II, the time scale of nanocluster formation
namic properties of small Si clusters within a tight- in typical sources ranges from a fraction of a millisecond
binding molecular-dynamics scheme. They confirmed to a few milliseconds. On this time scale, clusters may
previous results on the thermodynamics of very small not be able to reach the minimum free-energy structure,
clusters found by means of empirical many-body poten- thus remaining trapped in some metastable configura-
tials 共Stillinger and Weber, 1985; Blaisten-Barojas and tion that can have a very long lifetime, especially when
Levesque, 1986; Tchofo-Dinda et al., 1995兲, and also con- the clusters are further cooled down after their solidifi-
sidered larger sizes. Their canonical Monte Carlo simu- cation.
lations revealed that the melting point of Si clusters In studying the formation process of solid clusters in
changes dramatically when the global-minimum struc- contact with a thermal bath, such as the inert-gas atmo-
tures change from prolate and cagelike 共for N = 17 in this sphere in inert-gas aggregation sources, we can think of
study兲 to an atom-centered and nearly spherical mor- two alternative models. In both models, clusters grow
phology. The nearly spherical clusters present a much mainly by the addition of single atoms 共de Heer, 1993兲.
broadened melting region, extending from 750 to In the first model 共Sec. V.A兲, which is suited for high
1300 K. This is because, in nearly-spherical structures, growth temperatures, the cluster solidifies after its
the cluster core is more tightly bonded than the surface growth is completed, that is, at a further cooling stage
atoms, and a much higher temperature is needed to dis- taking place outside the growth chamber. In this case,
order it. In the range 650⬍ T ⬍ 1050 K, the nearly the final cluster structure does not depend on the kinet-
spherical clusters keep their structure, although there is ics of the growth process, because the cluster remains a
a noticeable surface diffusion. After that, melting can liquid droplet while growing, but rather depends on the
take place via two pathways. The first possibility is that, kinetics of the cooling after growth, which may take
as T increases, the clusters develop to the prolate mor- place on time scales like those discussed in Sec. V.A,
phology up to 1200 K, then break into subunits, which namely, in the range of 1 – 10−2 K / ns. This model will be
finally become less and less stable until the clusters dis- referred to as the liquid-state growth model. It is simu-
order completely. The other possibility is that the clus- lated by freezing a liquid droplet until it solidifies, usu-
ters develop from quasispherical to prolate to molten ally at constant N and decreasing T. In fact, there are
oblate structures. Atoms in prolate cagelike structures systems 共such as the noble gases兲 in which evaporation
are more stable than the surface atoms of the nearly of atoms is non-negligible at temperatures close to the
spherical structures. The melting of cagelike structures melting point, because melting and boiling temperatures
often accompanies the overall deformation and frag- are close to each other. Evaporating atoms can thus play
mentation of the cage framework. Thus a much higher an important role even in the cooling of solid clusters. In
temperature is needed to break the cage, but the whole contrast, metals present huge differences between melt-
When simulating cluster freezing, the relevant param- ration method let the cluster evaporate atoms in a simu-
lation at constant energy. They considered 380 clusters
eter is the rate rc at which the temperature T is rescaled,
in order to mimic a thermal contact with a cold atmo- in the range 160⬍ N ⬍ 2200, finding that there was a
sphere. For example, the cluster can be cooled down by transition at increasing size from icosahedra to a mixture
of structures 共decahedron, fcc, hcp, and icosahedron兲.
small steps ␦T at each time interval ␦t so that rc
The transition did not depend on the cooling method,
= ␦T / ␦t. In an inert-gas atmosphere, one can estimate
and took place for N ⯝ 450. This is lower than the tran-
that a cluster of radius R and area Aeff = 4R2 will collide
sition size 共750 atoms兲 observed in experiments on argon
with gas atoms with a frequency exp G
given by clusters 共Farges et al., 1986兲, but it is closer than any
PGAeff other estimate based on total energy optimization, thus
exp
G
⬃ 共43兲
冑2 m G k B T G , indicating the possible presence of kinetic trapping ef-
fects. Moreover, calculated and experimental diffraction
where PG and TG are the pressure and the temperature, patterns were in good agreement. Besides pure clusters,
respectively, of the inert gas of mass mG. In the har- Ikeshoji et al. 共2001兲 considered binary Lennard-Jones
monic approximation, the energy loss is given by systems, finding that the formation of large icosahedra
was favored by the size mismatch. This finding may fur-
␦T ␦E nish a qualitative explanation of the experimental obser-
⬃ exp
G
, 共44兲
␦t 3NkB vation of large icosahedron clusters in binary 共metallic兲
where ␦E is the energy transfer at each collision, and systems 共Saha et al., 1997, 1999兲.
since Aeff ⬀ N2 and N ⬀ R3 we obtain ␦T / ␦t ⬀ 1 / R. Follow-
ing Westergren et al. 共1998兲, we can estimate that the loss 2. Silver clusters
for each collision 共for example with a helium atom兲 ␦E is
Baletto, Mottet, and Ferrando 共2002兲 studied the
1 – 10 meV. Using typical parameters for the gas, PG
freezing of Ag liquid nanodroplets by molecular-
⬃ 1 – 100 mbar, TG ⬃ 300 K 共Reinhard, Hall, Ugarte, and
dynamics simulations with realistic cooling rates rc in the
Monot, 1997; Koga and Sugawara, 2003兲 and considering
range 0.1– 5 K / ns. They made a systematic study of Ag
R ⬃ 1 nm, we have ␦T / ␦t in the range 0.01– 1 K / ns.
freezing at 130艋 N 艋 310, and in addition considered the
freezing at the icosahedral magic numbers 147, 309, 561,
1. Lennard-Jones clusters and 923. The latter simulations were made to investigate
Ikeshoji et al. 共2001兲 studied the freezing of Lennard- the possibility of obtaining large metastable Ag icosahe-
Jones clusters by molecular-dynamics simulations. Con- dra by freezing liquid droplets, in order to ascertain
trary to what happens for metals, the melting and boil- whether the liquid-state growth model could explain the
ing points of these clusters are rather close in experimental observation of metastable icosahedra by
temperature, so that the evaporation of atoms during Reinhard, Hall, Ugarte, and Monot 共1997兲.
the solidification process is non-negligible. Because of The results for 130艋 N 艋 310 are summarized in Fig.
that, Ikeshoji et al. 共2001兲 considered two ways of cool- 27. On a coarse-grained description, the energetic calcu-
ing clusters down. The thermostat method decreased lations by Baletto, Ferrando, et al. 共2002兲 showed that
temperature in a canonical simulation, while the evapo- icosahedral clusters are the best up to N ⯝ 170; then the
best structures are decahedral, except for the icosahe-
dral magic number N = 309, while fcc clusters become
17
Clusters may solidify during growth at constant tempera- competitive with the decahedra for N ⬎ 600. The freez-
ture after reaching a critical size. ing simulations of Baletto, Mottet, and Ferrando 共2002兲
1 147 5
309 4 1
561 2 2 1
923 1 4
5 147 5
309 3 2 FIG. 28. 共Color in online edition兲 Molecular-dynamics simula-
561 2 3 tion of silver cluster freezing. On the left, we show the initial
923 1 4 configurations of Ag liquid nanodroplets at magic icosahedral
numbers 共147, 309, 561, and 923兲, while on the right, there are
20 147 5 typical final structures obtained by cooling at 1 K / ns: from top
309 2 1 2 to bottom, 147-atom icosahedron; 309-atom icosahedron; a
561 1 3 1 decahedron at 561 关strongly asymmetric and with an island on
hcp stacking above 共Baletto and Ferrando, 2001兲兴; a fcc poly-
923 1 3 1
hedron at 923.
gave the following results. At rc = 1 K / ns, particles so- Reinhard, Hall, Ugarte, and Monot 共1997兲, who did not
lidified as icosahedra in the range 135⬍ N ⬍ 165. Around find strong evidence of small icosahedra, while they ob-
N = 165 there was a transition to decahedron clusters, served a dominant percentage of icosahedra at large
which were the most frequent for 170⬍ N ⬍ 245. About sizes. Therefore, one can rule out the liquid-state growth
20% of the runs gave fcc structures in this range, and a model as an explanation for the outcome of this experi-
ment.
few icosahedron clusters were formed. For 245⬍ N
⬍ 310, the dominant structures at the end of the freezing
were icosahedra, but fcc clusters were also common, es- 3. Gold clusters
pecially in the range N ⬃ 250– 260 and N ⬃ 280– 300, in Chushak and Bartell 共2001a, 2001b兲 studied the solidi-
which they made up more than 50%. At slower cooling fication of Au nanoclusters by molecular-dynamics simu-
rates, rc = 0.12 K / ns, the percentage of fcc and icosahe- lations. However, their method is rather different from
dron particles in the range 170⬍ N ⬍ 245 dropped prac- that applied to Ag clusters by Baletto, Mottet, and Fer-
tically to zero, indicating that decahedron clusters are rando 共2002兲. Chushak and Bartell 共2001a, 2001b兲
likely to be the most favored from the thermodynamic started from high-T liquid clusters of rather large sizes
point of view in this size range. On the other hand, at 共459, 1157, and 3943 atoms兲. These clusters were then
faster cooling rates, rc = 5 K / ns, the percentage of fcc cooled down very quickly, at a rate rc = 5 ⫻ 104 K / ns, to a
clusters in the range 245⬍ N ⬍ 310 decreased in favor of temperature of about 700 K, at which their most stable
decahedron clusters, while the dominant proportion of form is solid. At this temperature, production runs of
icosahedra remained practically constant. 1 ns were performed. After that, clusters were further
From the freezing results at the icosahedral magic quenched down to 300 K, again with a fast rate
numbers 147, 309, 561, and 923, it was possible to extract 共300 K / ns兲. As a result of this cooling procedure
the following tendency 共see Table II and Fig. 28兲. The Chushak and Bartell found that icosahedron clusters
percentage of icosahedral structures at the end of the were preferentially produced, even though they should
freezing process decreased with cluster size for all cool- not be the lowest-energy structures at these sizes 共see
ing rates, passing from 100% at N = 147 to less than 20% Baletto, Ferrando, et al., 2002兲. In this case, icosahedron
at N = 923. There was no evidence of changes in the re- clusters were produced with high probability during
sults when rc ranged within 1 – 20 K / ns, probably indi- freezing because of the width of the icosahedron funnel
cating that these rates are sufficient to mimic a freezing 共Doye, 2004兲 with respect to the funnels leading to ei-
process taking place close to equilibrium. ther close-packed or decahedral structures. This is a ki-
In summary, the simulations showed that it is not pos- netic trapping effect, which is stronger at rapid cooling
sible to avoid the formation of a large percentage of rates, and agrees with the results on Ag freezing by Bal-
small icosahedra 共2 – 3 nm diameter兲 if freezing takes etto, Mottet, and Ferrando 共2002兲.
place after the growth is completed. Moreover, the prob- Nam et al. 共2002兲 have studied the mechanism by
ability of forming large icosahedra by freezing liquid Ag which metastable gold icosahedron clusters are frozen
droplets with realistic cooling rates is small. Both find- out of nanodroplets using molecular-dynamics simula-
ings are in contrast with the experimental results of tions within the embedded-atom model. Their simula-
FIG. 35. 共Color in online edition兲 Ag38 growth simulation re- FIG. 36. 共Color in online edition兲 Cu38 growth simulation re-
sults. In the top row, snapshots from a simulation at T sults. Symbols as in Fig. 35. In the top row, snapshots from a
= 200 K are shown at different sizes. The structures of the Cu simulation at T = 400 K are reported. Again, the snapshots
snapshots pertain to the global minima up to N = 33; then reproduce the global minima up to N = 33. On the contrary, the
growth is kinetically trapped into defected decahedron struc- growth structure at N = 38 is not the global minimum but a Dh,
tures, which are neither energetically nor entropically favored. which is entropically favored at this temperature. Around
The graph shows the structural frequencies fTO, fDh, fLS of 200 K, there is a strong kinetic trapping into Dh structures
different structures at N = 38 and at different growth tempera- formed at smaller sizes. At intermediate temperatures the TO
tures: open stars, truncated octahedra; solid stars, decahedra; structure is preferentially grown; at high T, Dh structures again
triangles, low-symmetry structures. The lines are only guides to prevail due to entropic effects. Adapted from Baletto et al.,
the eyes. At low temperatures, strong kinetic trapping into 2004
decahedral structures occurs. This is followed by an interme-
diate temperature regime where the three structural motifs are
essentially equally likely. At high temperatures, entropic ef- interesting behavior takes place around for Pt55, as an-
fects favor decahedral and low-sym-metry structures at the ex- ticipated in Sec. V.A.4, with the probable growth of ro-
pense of the truncated octahedron. Adapted from Baletto et sette structures, either because of kinetic trapping in in-
al., 2004. complete icosahedral structures formed at lower sizes,
or because of the onset of entropic effects at high tem-
peratures.
as can be seen in Fig. 34. The magic sizes are 13, 19, 25, A complex interplay of thermodynamic and kinetic
40, 43, 46, 49, and 55, with 13, 19, and 55 being of special effects takes place in the growth simulations of Ag38 and
stability. The sequences are well reproducible over a Cu38 共Baletto, Rapallo, et al., 2004兲. At this size, the glo-
wide range of growth temperatures. The main difference bal minimum is a truncated octahedron, which is in com-
between Ni and Cu is that in Ni it is easier to obtain petition with a series of defected decahedron structures
truncated octahedra of 38 atoms, even at relatively low 共mostly based on decahedra of 23 atoms covered by is-
temperatures 共400 K兲. In this case, growth continues lands兲, and in the case of Ag, with a low-symmetry struc-
with the cluster trapped in non icosahedral structures. ture that is neither a defected decahedron nor a close-
Growth sequences for Ag show the same kind of struc- packed cluster. In the case of copper, these decahedron
tures, but they are reproducible over a narrower tem- structures become favored over the truncated octahedra
perature range. In contrast, the growth sequences of Au at temperatures around 350 K, because of entropic ef-
reveal completely different magic sizes. Icosahedral fects. Moreover, for sizes just below N = 38, the global
structures are completely unfavored. The minima at N minima are defected decahedra in both Ag and Cu. For
= 13 and 19 are absent, replaced by peaks at N = 16 and these reasons, the truncated octahedron is not likely to
22. At N = 30 we find a decahedral minimum, which sur- be grown in the simulations. Performing several simula-
vives up to T ⬃ 300 K. At higher temperatures the clus- tions at T = 200, 250, 300, 350, and 400 K, and observing
ters oscillate among different structures over a time the structures grown at N = 38, one obtains the results
scale shorter than dep so that they can be considered reported in Figs. 35 and 36. At 200– 250 K, kinetic trap-
either melted or quasimelted. There is no evidence of ping into decahedron structures is the fate of essentially
entropic effects favoring the transition to icosahedral all simulations, so that the magic structure never coin-
structures. Finally, Pt and Pd show an intermediate be- cides with the global minimum, which is also the free-
havior between Cu, Ni, and Ag on the one side, and Au energy minimum in this temperature range. This kinetic
on the other. For Pd, there is a minimum at N = 13, but trapping is due to the fact that the global minima in the
there is no evidence of any other magic size up to the range 30–37 atoms are decahedral 共with the single ex-
Ih55, which is likely to be grown. In Pt, minima are found ception of Cu37兲. In the interval 300– 350 K, kinetic trap-
at N = 13 共as in Cu兲 and 22 共as in Au兲. At high T, it is ping becomes less effective, even if it is still somewhat
possible to grow truncated octahedra of 38 atoms. Very present. In this range, the truncated structures are still
C. Coalescence of nanoclusters
and Mullins, 1965; Jensen, 1999兲 via surface diffusion. structures, such as the icosahedra, and favoring the for-
Finally, the coalescence of two solid clusters 共simulated mation of low-symmetry structures. Finally, bond direc-
also by Zhu, 1996 for Cu clusters兲 is a complex phenom- tionality is crucial in semiconductor clusters and in some
enon, which takes place on a slow time scale and may metals, too.
involve either the formation of a single domain cluster Several examples have shown that the interplay of en-
or of complicated structures presenting grains. This de- ergetics, thermodynamics, and kinetics is crucial, and
pends on size and structure of the initial clusters, at vari- that a satisfactory explanation of the experimental out-
ance with the previous cases. Moreover, the nucleation comes is very often impossible on the basis of energetic
of a critical island on the surface can govern the rear- considerations alone. This can have deep consequences
rangement kinetics 共Combe et al., 2000兲. for the very important issue of controlling the shapes of
Recently Hendy et al. 共2003兲 simulated the coales- the produced nanoclusters, which is of great technologi-
cence of free lead clusters in the microcanonical en- cal importance. Given that the interplay of the three
semble, without coupling the clusters to a thermostat. factors is crucial, each one is extremely interesting by
This seems to be the most appropriate method when itself and poses stimulating theoretical challenges.
dealing with free clusters produced in inert-gas aggrega- The development of reliable methods for modeling
tion sources. In fact, when two clusters come into con- the energetics of nanoclusters is a rapidly developing
tact, many new bonds form, causing a considerable re- field, both from the point of view of ab initio calcula-
lease of surface energy. This can cause a noticeable tions, well suited for precise calculations on small sys-
temperature increase 共more than 100 K for clusters of tems, and from the point of view of semiempirical mod-
N ⯝ 500兲. Since cooling rates are less than 1 K / ns 关see eling, which is needed to treat larger systems and to
Eq. 共44兲兴, and the initial stage of coalescence develops in simulate long time scales. In cluster science, these ap-
a few ns 共see Figs. 43 and 44兲, the inert gas is not likely proaches are complementary and are both necessary.
to affect the process strongly by taking energy away. The Since the best structure of a cluster of given size and
temperature increase makes the coalescence process composition is generally unknown, the semiempirical
much faster, by enhancing surface diffusion. Hendy et al. modeling, which has a much lower computational cost, is
共2003兲 considered the coalescence of two solid surface- the starting point for selecting good candidates for sub-
reconstructed icosahedral clusters 共Hendy and Hall, sequent ab initio local structural optimization. We have
2001兲 of 565 atoms. They found that, depending on the seen that there are already several examples in the lit-
initial temperature and the sizes of the two clusters, the erature showing that this approach is extremely fruitful,
final aggregate could be either solid or liquid. When the and now the challenge is to extend it to large sizes and
final temperature Tf of the resulting cluster of 1130 at- complex systems 共for example, nanoalloys兲. The search
oms was below Tm of the Ih565, the coalescence took for good structural candidates is performed by global
place through solid states. On the other hand, when Tf optimization methods. The literature on these methods
was above Tm of the resulting cluster of 1130 atoms, the and their applications to clusters has exploded in the last
final cluster was liquid. Finally, when Tf was in between few years; several different procedures have been pro-
the two melting temperatures, the aggregate melted at posed, with important progress towards the understand-
first and solidified again at a later stage. ing of the requirements for building up efficient global
optimization algorithms. The main point here is that the
VI. CONCLUSIONS AND PERSPECTIVES most efficient algorithms work after transforming the
original PES to a multidimensional staircase. In the field
In this review we have tried to present an overview of of global optimization, there is still the need to develop
the physical properties of nanoclusters, with the aim of algorithms for complicated systems and large sizes. The
showing the interplay of energetic, thermodynamic, and latter task is, however, limited by the intrinsic NP-hard
kinetic factors in building up the structures that are pro- nature of the global optimization problem itself 共see
duced in the experiments or observed in the simulations. footnote 3 and Wille and Vennik, 1985兲. Thus there is no
We hope that we have demonstrated that the physics of hope in optimizing very large clusters, although good
nanoclusters can be understood only by taking into ac- putative global minima are found by the present algo-
count all three factors and relating them to the features rithms by exploring only a very small fraction of the
of the interparticle potential. Among these features, the huge number of local minima. The reason why these
potential range is always a guideline for understanding algorithms work lies in the features of the PES, which
the qualitative features of structural properties and may present funnels in which optimization is fast, and in
transformations. For example, we have seen that soft the favorable transformation of the thermodynamics of
interparticle interactions admit noncrystalline clusters as the system when working on the staircase PES.
minimum-energy isomers. In contrast, for sticky inter- The thermodynamics of nanoclusters is a very active
particle potentials, crystalline structures are energeti- research field, with several problems under debate. For
cally favored, but at the same time kinetic trapping phe- example, the relation between elementary interactions
nomena are enhanced. The latter often cause the growth and the type of phase changes in clusters is still to be
of noncrystalline structures in the actual experiments. In understood to a large extent for realistic model poten-
metallic systems, the bond-order/bond-length correla- tials. Moreover, the effect of chemical composition on
tion plays a crucial role in destabilizing some cluster melting and on structural transitions has been the sub-
ject of very few studies. Finally, the approach of the bulk Aziz, R. A., F. R. W. McCourt, and C. C. K. Wong, 1987, Mol.
limit is not yet well understood. Each of these problems Phys. 61, 1487.
poses complex theoretical and computational chal- Bacelo, D. E., R. C. Binning, and Y. Ishikawa, 1999, J. Phys.
lenges. Chem. A 103, 4631.
The study of the growth kinetics of nanoclusters is a Bachels, T., H. J. Güntherodt, and R. Schäfer, 2000, Phys. Rev.
field that is just starting to develop. Here, a systematic Lett. 85, 1250.
study of small systems by the available methods is still to Bachels, T., and R. Schäfer, 2000, Chem. Phys. Lett. 324, 365.
be performed. Moreover, new methods should be devel- Baguenard, B., M. Pellarin, J. Lermé, J. L. Vialle, and M.
oped, first of all to extend the size of the simulated sys- Broyer, 1994, J. Chem. Phys. 100, 754.
tems and the time scale of the simulations, and then to Bailey, M. S., N. T. Wilson, C. Roberts, and R. L. Johnston,
treat the formation of clusters in complex environments, 2003, Eur. Phys. J. D 25, 41.
Baletto, F., 2003, Ph.D. thesis 共Universita di Genova兲.
such as formation in liquid solutions or on surfaces, in-
Baletto, F., J. P. K. Doye, and R. Ferrando, 2002, Phys. Rev.
teraction with passivating agents and adsorbed mol-
Lett. 88, 075503.
ecules, and so on.
Baletto, F., J. P. K. Doye, C. Mottet, and R. Ferrando, 2003,
In conclusion, we hope that our review article has Surf. Sci. 532, 898.
given at least some idea of the present development of Baletto, F., and R. Ferrando, 2001, Surf. Sci. 490, 361.
the fascinating and lively subject of cluster science. Baletto, F., R. Ferrando, A. Fortunelli, F. Montalenti, and C.
Mottet, 2002, J. Chem. Phys. 116, 3856.
ACKNOWLEDGMENTS Baletto, F., C. Mottet, and R. Ferrando, 2000a, Surf. Sci. 446,
31.
The authors are grateful to Jonathan Doye, Alessan- Baletto, F., C. Mottet, and R. Ferrando, 2000b, Phys. Rev. Lett.
dro Fortunelli, Ignacio Garzón, Hellmut Haberland, 84, 5544.
Roy Johnston, Andrea Levi, Christine Mottet, Arnaldo Baletto, F., C. Mottet, and R. Ferrando, 2001a, Phys. Rev. B
Rapallo, and Giulia Rossi for their help and suggestions. 63, 155408.
Baletto, F., C. Mottet, and R. Ferrando, 2001b, Eur. Phys. J. D
The authors acknowledge financial support from the
16, 25.
Italian MIUR under the project 2001021133. R.F. ac-
Baletto, F., C. Mottet, and R. Ferrando, 2002, Chem. Phys.
knowledges financial support from CNR for the project
Lett. 354, 82.
SSA-TMN in the framework of ESF EUROCORES- Baletto, F., C. Mottet, and R. Ferrando, 2003, Phys. Rev. Lett.
SONS. 90, 135504.
Baletto, F., A. Rapallo, G. Rossi, and R. Ferrando, 2004, Phys.
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