Article

pubs.acs.org/JPCA

Density Functional Study of Neutral and Charged Silver Clusters Agn

with n = 2−22. Evolution of Properties and Structure
Michael L. McKee*,† and Alexander Samokhvalov*,‡
†
Department of Chemistry and Biochemistry, 179 Chemistry Building, Auburn University, Auburn, Alabama 36849, United States
‡
Department of Chemistry, 315 Penn Street, Rutgers University, Camden, New Jersey 08102, United States
*
S Supporting Information

ABSTRACT: Geometries and electronic properties of neutral Agn, cationic Agn+,

and anionic Agn− silver clusters with n = 2−22 were investigated by density
functional theory (DFT) with M06 functional. For neutral clusters, transition
from planar to “empty cage” structure occurs at n = 7, “empty cage” to “cage with
one Ag atom” at n = 18, and to “cage with two Ag atoms” at n = 22. For lowest-
energy Agn clusters, Ag8 and Ag18 show lowest polarizability due to closed-shell
valence electron configurations 1S2/1P6 and 1S2/1P6/1D10. High stability of Ag8
is manifested in small dissociation energies of Ag9 to Ag8 plus Ag1 and Ag10 cluster
to Ag8 plus Ag2. Cluster Ag20 with configuration 1S2/1P6/1D10/2S2 is stable due
to low dissociation energy of Ag21 to Ag1 and Ag22 to Ag2. Cationic clusters with
even n namely Ag10+ (9 valence electrons), Ag16+ (15 valence electrons), and
Ag22+ (21 valence electrons) dissociate to Ag1 and closed-shell Ag9+ (1S2/1P6),
Ag15+ (1S2/1D10/2S2) and Ag21+ (1S2/1P6/1D10/2S2). For odd n, Ag11+ and Ag17+
dissociate to Ag2 and closed-shell Ag9+ and Ag15+. For anionic clusters Agn−,
cohesion energy Ecoh and binding energy (BE) show maxima at n = 7 and n = 17 due to stable Ag7− and Ag17− clusters. Small
Agn− clusters (n = 4−11) with even n (except n = 8) have lower dissociation energy for loss of Ag1 while those with odd n have
lower dissociation energy for loss of Ag2. For n = 12−22, all clusters have lower dissociation energy for loss of Ag1.

1. INTRODUCTION nonplanar), and energies. The M06 was concluded to be one of

Small to medium size silver clusters Agn where n ≈ 2−20,
feature quite interesting optical,1 electronic,2 and magnetic3
properties, and they find applications in photonics,4 catalysis,5
biomedical technology.6 Small silver clusters have been a topic
of much interest in recent decade, because their chemical and
physical properties change significantly when cluster size
increases. Understanding changes in geometry of small silver
clusters versus their size may lead to design of new
nanodevices, more efficient nanostructured catalysts, fluores-
cent markers, and so forth. The properties of silver clusters
have been understood less than the properties of gold clusters
of the same size.7 Quantum chemical computations of silver
clusters are of interest, because they can reveal new stable
structures that are yet to be obtained by experiment.
For neutral silver clusters, many quantum chemical
computations have been reported. Tiago et al.8 computed
electronic and optical excitations in small neutral Agn clusters
with n = 1−8 by density functional theory (DFT) in
comparison to many-body theories within an ab initio
pseudopotential framework. Harb et al.1 reported a joint
computational (time-dependent density functional theory, TD-
DFT) and experimental study of absorption spectra of neutral
medium-size Agn clusters with n = 4−22. Recently, Duanmu et
al.9 studied all possible isomers for small clusters with n = 5−7
using 42 exchange−correlation functionals to assess geometries
(e.g., internuclear distances), structures (e.g., planar versus
the best functionals for computation of properties of cationic
and anionic silver clusters.9 Chen et al.10 used DFT followed by
high level coupled cluster CCSD(T) calculations to optimize
geometry of Agn clusters with n < 100. Yang et al.11 optimized
structures of neutral Agn clusters with n = 13−160 using a
modified dynamic lattice searching (DLS) method.
Cationic silver clusters Agn+ have been frequently studied by
experiment, and they are of major interest in photonics,
biomedicine, and catalysis. Small cationic Agn+ clusters are
easily obtained in aqueous solutions including those at ambient
conditions,12−14 which is in stark contrast with neutral small
Agn clusters that require cryo-matrix of inert gas to remain
stable.15,16 In heterogeneous catalysis, silver clusters supported
on metal oxides are of significant interest in ethylene
epoxidation.17 As relevant to catalysis, computational studies
were utilized to study interactions of cationic silver clusters with
small molecules such as hydrogen,18 carbon monoxide,19
chlorine,20 oxygen,21 and so forth. Duanmu et al.9 studied
small clusters Ag2+ through Ag7+ by DFT/M06 and CCSD(T).
Gamboa et al.22 reported computations of geometry and
electronic properties of small neutral Agn versus cationic Agn+
and anionic Agn− clusters with n = 3−15 using generalized
Received: April 25, 2017
Revised: June 5, 2017
Published: June 6, 2017

© 2017 American Chemical Society 5018 DOI: 10.1021/acs.jpca.7b03905

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Figure 1. Structures of lowest-energy neutral clusters Ag2 through Ag19.
gradient approximation (GGA) functional by Perdew, Burke,
and Ernzerhof (PBE).
Computations of anionic silver clusters Agn− are more
seldom than those of neutral clusters. Matulis et al.23 tested the
set of the DFT functionals to calculate vertical detachment
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energy (VDE), excitation energies Te for transition from
ground to the first excited state, bond lengths re, and vertical
ionization potentials (IPv) of anionic Ag2− versus neutral Ag2
clusters and used the DFT with S2LYP functional24 to calculate
geometries of larger Ag11− and Ag12− clusters. Liao et al.25
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Figure 2. Structures of lowest-energy neutral clusters Ag20 through Ag22.
calculated geometries, ionization potentials (IPs) and electron
affinities (EAs) of anionic Agn− versus neutral Agn clusters with
n = 2−25 using DFT with functionals BP86, revPBE (revised
Perdew−Burke−Ernzerhof functional), and B3LYP. Duanmu et
al.9 compared an accuracy of M06 functional and CCSD(T)
versus experimental data for small clusters Ag2− through Ag7−.
It would be of interest to find the DFT functional that allows
reliable calculations of geometry and electronic properties of
both neutral and charged silver clusters of variable size. The
M06 functional has been parametrized for transition metals and
nonmetals and tested successfully against multiple databases
including thermochemistry, kinetics, noncovalent interactions,
transition metal bonding, and so forth.26 As pertinent to
nanoclusters, the M06 functional has been validated to predict
the planar-to-3D transition in anionic gold clusters.27 To our
knowledge, the M06 functional has not been used to calculate
geometry and electronic properties of medium-size neutral or
charged silver clusters with n > 12.
Recently, we successfully used the M06-2X functional with
DFT to calculate energy and geometry of adsorption sites28 in
metal−organic frameworks (MOF). Herein, we describe the
systematic DFT computations with M06 functional to
determine optimized geometry, IP, EA, cohesion energy
(Ecoh), binding energy (BE) of Ag atom, and dissociation
energy for loss of Ag1 monomer or Ag2 dimer for neutral Agn,
cationic Agn+ and anionic Agn− clusters with n = 1−22.
2. COMPUTATIONAL DETAILS
All structures were optimized at the M06 level26 with the
Stuttgart small core scalar relativistic effective core potential29
(SDD) with the ECP28MWB basis set for Ag (contracted to
6s5p1d). Vibrational frequencies were computed to determine
the nature of the stationary points and to make zero-point and
thermal corrections to 298 K. The Gaussian09 program
system30 was used for all geometry optimizations and frequency
calculations.
3. RESULTS AND DISCUSSION
3.1. DFT Computations of Geometry of Neutral Silver
Clusters Ag1 through Ag22. We have optimized geometry of
neutral clusters Agn for n = 1−22 of all possible structures using
the M06 functional, as well as cationic clusters Agn+ and anionic
clusters Agn− for the same range of n. Table S1 shows notations,
charge, symmetry, electronic and spin states, energy, entropy
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and heat capacity computed at the M06/SDD(Ag) level of
theory. Table S2 shows Cartesian coordinates for Agn clusters
with n = 2−22 (neutral, cation, and anion) optimized at the
M06/SDD(Ag) level. Small neutral silver clusters with n < 12
were extensively studied by the DFT calculations, for
example,1,8,23 including the M06 functional.9 Our main interest
is to study the larger clusters with n = 12−22. Structures of all
computed neutral clusters for Ag12 through Ag22 are in the
Supplementary Figures S1−S10; in our search of lowest-energy
structures, we considered all of lowest-energy geometries of
neutral silver clusters reported in ref 10.
Figure 1 shows computed lowest-energy structures for
neutral Ag2 through Ag19 clusters. As n increases, one can see
a progression in the lowest-energy structures from planar to
“empty cage” (transition from Ag6 to Ag7). This finding is
consistent with reported22 change in geometry of the lowest-
energy neutral smaller Agn clusters with n = 1−15, where three-
dimensional cage structure becomes of lower energy than its
isomeric planar structure at n = 7, as determined by the first-
principles molecular orbital (MO) approach with the exchange
correlation included within a generalized gradient DFT
formalism.31 In Figure 1, when n further increases for Agn
clusters, there are progressions from empty cage structure to
the structure with one Ag atom in cage (at Ag18).
Figure 2 shows lowest-energy structures of the largest
clusters Ag20 through Ag22. Within the size range n = 18−22,
the transition occurs from “cage with one Ag atom” to “cage
with two Ag atoms” (for Ag22 cluster). To our knowledge,
structural transitions of lowest-energy cluster from empty cage
to “one atom in cage” and further to “two atoms in cage” have
not been systematically investigated.
To draw correlations “structure/electronic properties” for
neutral silver clusters, attention was paid to highly symmetric
structures with zero, one or two silver atoms located entirely
inside the cage; these “internal” silver atoms are fully
coordinated with other silver atoms.
Table 1 shows correlations between the energy difference
(kcal/mol) for neutral Agn clusters of different symmetry. The
energy of isomeric Agn clusters with the given number of Ag
atoms inside the cage is shown versus computed total energy of
lowest-energy cluster Agn. When several clusters existed for the
given n and the given geometry, for example, cage with one Ag
atom, the lowest energy structure was chosen. Notations of
structures are the same as in Table S1 and in Supplementary
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Table 1. Geometry and Total Energy (kcal/mol) of Neutral

Agn Clusters versus the Lowest-Energy Agn Isomer for Planar
Structure and Cage with Zero, One, or Two Ag Atoms
empty
planar cage, cage with one Ag cage with two Ag
structure/ structure/ atom inside, atoms inside,
cluster energy energy structure/energy structure/energy
Ag6 Ag6A 0.0 Ag6B 3.6
Ag7 Ag7C Ag7A 0.0
14.0
Ag12 Ag12L Ag12A 0.0
18.4
Ag13 Ag13A 0.0 Ag13H 21.9
Ag14 Ag14A 0.0 Ag14G 22.6
Ag15 Ag15A 0.0 Ag15E 15.4
Ag16 Ag16A 0.0 Ag16D 4.5 Ag16K 43.8
Ag17 Ag17A 0.0 Ag17B 2.4
Ag18 Ag18B 0.7 Ag18A 0.0 (lowest-
energy cluster with
one Ag atom)
Ag19 Ag19A 0.0 Ag19G 13.8
Ag20 Ag20A 0.0 Ag20D 18.3
Ag21 Ag21A 0.0 Ag21B 2.7
Ag22 Ag22E 15.8 Ag22A 0.0 (lowest-
energy cluster
with two Ag
atoms)

Figures S1−S10. Planar structures are absent among lowest-

energy clusters starting at n = 13 and higher. From Ag13 to Ag18,
there is a steady increase in stability of cage with one Ag atom
relative to empty cage (with zero Ag atoms). When one Ag
atom is located inside a cage, such neutral Agn cluster is of
lowest energy (shown as zero energy in Table 1) among
isomeric Agn clusters for n = 18, 19, 20 and 21.
When two Ag atoms are inside a cage, such neutral Agn
cluster is of lowest energy at n = 22. Thus, analysis of symmetry
of neutral Agn clusters results in the “transition” regions at n =
7, n = 18, and n = 22, where significant changes in electronic
properties are anticipated, based on computed lowest energy
structures.
3.2. DFT Computations of Electronic Properties of
Neutral Silver Clusters Ag1 through Ag22. Electronic
properties of silver clusters can be assessed through IP and EA.
Figure 3a shows calculated IP for each lowest-energy neutral
cluster (Figures 1 and 2) in the range Ag1 through Ag22.
Computed IP for Ag1 at 177.1 kcal/mol is in good agreement
with experimental value32 at 7.57 eV or 174.6 kcal/mol (1.4%
error). Computed IP for linear dimeric cluster Ag2 at 179.6
kcal/mol is also in good agreement with experimental value32 at
7.65 eV or 176.4 kcal/mol (1.8% error). For larger silver
clusters, various linear, planar or 3D structures were found by
calculations, while experimental data could have been obtained
with specimens containing mixture of geometric isomers, so
comparisons with published computed data are preferred. In
Figure 3a, several trends can be seen for the IP. First, the IP
steadily decreases as n increases for very small clusters with n =
2−5. This finding is in agreement with Gamboa et al.22 who
used the MO approach with exchange and correlation
functionals as a generalized gradient approximation (GGA)
within the DFT for small Ag1−Ag15 clusters, and found a
decrease of the IP within n = 1−3. Second, for n > 4,
oscillations of the IP are observed for Agn clusters with even/
odd number of silver atoms with the maxima for even n,
consistently with other reports.8,22,33 An increased value for the
5021
Figure 3. Calculated energies for removal or attachment of electron
from lowest-energy neutral clusters Ag1 through Ag22. (a) IP. (b) EA.
IP for neutral Agn clusters with even n is due to filled valence
electronic shells forming lower energy singlet state, compared
to higher energy state with one unpaired electron in valence
shell (for odd n). Third, a “first minimum” in the IP is found at
n = 9, and easy ionization of neutral Ag9 cluster results in stable
cationic Ag9+ cluster with eight valence electrons. Neutral Ag8
cluster with eight valence electrons is known to be of an
enhanced stability due to the so-called magic number34 n = 8,
which is related to closed valence shell with 1S2/1P6 electronic
configuration. Further at n = 12−17, the IP shows “even/odd”
oscillations without general increase or decrease trend,
consistently with empty cage structure (Table 1). Finally, the
IP decreases within n = 18−22 forming the “second minimum”
at n = 21 in Figure 3a. To our knowledge, such decrease in the
IP was not reported for silver clusters with n = 18−21, but it is
consistent with transition from cage with one Ag atom structure
to Agn clusters with cage with 2 Ag atoms (Figures 1 and 2 and
Table 1). The second minimum at n = 21 in Figure 3a is
consistent with easy ionization of neutral Ag21 cluster to stable
cationic Ag21+ cluster with 20 valence electrons. The obtained
stable cationic Ag21+ cluster is isoelectronic, by the number of
valence electrons, with neutral Ag20 cluster featuring “magic
number” n = 20, closed valence subshell with configuration
1S2/1P6/1D10/2S2 and enhanced stability.35
EA (Figure 3b) is reminiscent of a mirror image of the IP as a
function of n: when the IP has a maximum, the EA has a
minimum, consistently with other reports, for example, study of
silver clusters22 with n = 1−14. For empty cage clusters, local
maximum of the EA at n = 9 is consistent with first minimum in
the IP at n = 9 in Figure 3a. For cage with one Ag atom
structures, global maximum of the EA at n = 17 is consistent
with high electron affinity of neutral Ag17 cluster that forms
stable anionic Ag18− cluster with closed-shell valence electron
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configuration 1S2/1P6/1D10. The minimum in the EA at n = 20
is consistent with high stability of neutral Ag20 cluster with
closed-shell valence electron configuration 1S2/1P6/1D10/2S2.
Numerically, both IP and EA are defined on “per cluster”
basis. We wanted to study how the other electronic properties
of silver clusters depend upon n in the range n = 2−22, when
assessed on “per atom” basis. The cohesion (or cohesive)
energy Ecoh is defined as the energy needed to form a cluster
from the individual (noninteracting) atoms, and Ecoh is
calculated per atom in the cluster. Fournier et al.33 reported
that cohesive energy of lowest-energy neutral Agn clusters
steadily increased within n = 2−12. Figure 4a shows calculated
Figure 4. Energy of interactions of Ag atoms for lowest-energy neutral
clusters Ag2 through Ag22. (a) Ecoh. (b) BE.
cohesion energies Ecoh (average binding energy per Ag atom)
for lowest-energy neutral clusters Agn within n = 2−22. In
Figure 4a, the Ecoh increases in general when n increases as
expected, reflecting the larger gain in the energy due to multiple
new bonds in the cluster formed by many individual atoms,
consistently with published data.3,33 In Figure 4a, the first
anomaly or “first maximum” in Ecoh is at n = 8 due to an
enhanced stability of Ag8 cluster with valence 1S2 /1P6
configuration. For “cage with one Ag atom” structures, the
“second maximum” at n = 20 is due to Ag20 cluster with closed
shell 1S2/1P6/1D10/2S2 configuration. Presence of the two
maxima in Figure 4a is illustrated with the two minima in Ecoh
at n = 9 and n = 21.
BE is defined as the energy change when one atom is added
to the cluster; it is one of critical properties to assess the degree
of stabilization of metal cluster, for example.36 Figure 4b shows
calculated BEs of Ag atom for lowest-energy neutral clusters
Agn as a function of n. The BE fluctuates for pairs “odd/even n”,
consistently with computational study22 of energy needed for
removal of silver atom from neutral clusters Ag1 through Ag16.
In Figure 4b, the lower BEs of neutral Agn clusters with odd n
(compared to even n) are due to lower stability of clusters with
odd number of valence electrons (half-filled orbitals) versus
clusters with even number of valence electrons (filled orbitals,
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singlet state). In addition to “even/odd oscillations” in Figure
4b, one can see the first minimum of BE at n = 9 and second
minimum at n = 21, consistently with minima for Ecoh in Figure
4a. In Figure 4b, global maximum in the BE for Agn clusters is
at n = 20 indicating an enhanced stability of neutral Ag20
cluster. Neutral sodium clusters Nan serve as model to predict
behavior of neutral Agn clusters, because each Na atom donates
one electron to the molecular orbitals (MOs) of the cluster.
Binding energy of neutral clusters Nan calculated for n = 10−25
showed global maximum37 at n = 20, in accord with our data
for Agn clusters in Figure 4b with global maximum in the BE at
n = 20.
Static electric dipole polarizability is another major electronic
property, which determines the dynamic response of atomic
system with bound electrons to external electric or magnetic
field. Quantitative analysis of polarizabilities of metallic clusters
(in units of cube of Bohr radius a0 per atom) often reveals a
strong dependence upon the structure of the cluster.38 Figure 5
Figure 5. Computed polarizability of lowest-energy neutral clusters
Ag2 through Ag22.
shows computed polarizability for lowest-energy neutral Agn
clusters within n = 2−22. In general, when each of the two
major structures (planar structure with n = 3 through n = 6 and
empty cage with n = 7 through n = 18) progressively increases
in size with the increase of n, polarizability of the cluster first
remains rather high, but then decreases. The two minima in the
polarizability in Figure 5 at n = 8 and n = 18 are consistent with
valence electron configuration 1S2/1P6 for neutral Ag8 cluster
and 1S2/1P6/1D10 for neutral Ag18 cluster. This indicates that
both low-polarizability, “rigid” neutral Ag8 and Ag18 clusters
feature closed valence electronic shells. The second minimum
at n = 18 for neutral Agn clusters in Figure 5 is consistent with
computed minimum in polarizability for neutral sodium Na18
clusters.37
Figure 6 shows computed HOMO−LUMO gap energies of
lowest-energy neutral clusters Ag1 through Ag22.
In general, computed HOMO−LUMO gaps in Figure 6
steadily decrease as n increases with the trend toward a zero
optical gap for bulk silver metal, as expected. The fluctuations
in HOMO−LUMO gap for Agn clusters with even n (larger
gap) and odd n (smaller gap) in Figure 6 are consistent with
published DFT calculations22,36 using functionals other than
M06. Clusters Agn with even n have all their valence electrons
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Figure 6. HOMO−LUMO gaps of lowest-energy neutral clusters Ag1

through Ag22.

paired which explains the higher stability (as well as lower

chemical reactivity in general) and larger bandgaps.36 In Figure
6, for “empty cage” Agn clusters (with n = 7−17) there is a
maximum in computed bandgaps at n = 8, consistently with
stable Ag8 cluster with closed shell 1S2/1P6 configuration. For
larger clusters “one Ag in cage” with n = 18−21, one can see the
maximum at n = 20, consistently with magic number35 and
electronic configuration 1S2/1P6/1D10/2S2 explaining an
enhanced stability and larger bandgap of Ag20 cluster with 20
valence electrons.
The lowest-energy neutral Ag18 cluster of one Ag in cage
structure (Figure 1) has valence electron configuration 1S2/ Figure 7. Diagram of molecular orbitals for lowest-energy Ag18 cluster.
1P6/1D10 and reminds in terms of number of valence electrons
the lowest-energy neutral Na18 cluster.37 The lowest-energy
neutral Ag18 cluster showed a global minimum in polarizability
curve (Figure 5) versus n and hence an enhanced stability.
Figure 7 shows the diagram of molecular orbitals (isosurfaces
generated by Gaussian program) for lowest-energy neutral Ag18
cluster denoted Ag18A in Table 1 and Table S1. The lowest-
energy MO of this neutral Ag18 cluster (which would be 1S
orbital) is strongly mixed with other orbitals to be identified;
only eight higher-energy filled MOs including the HOMO are
shown, as well as the LUMO.
Experimentalists studying small nanoparticles are often
frustrated to find out that none of the two nanoparticles are
of the same size; precise control of the size of small
nanoparticle or nanocluster is of importance. Dissociation of
neutral silver clusters Agn with selective formation of Agn−1 or
Agn−2 clusters would be attractive for synthesis of small clusters
with well-controlled number of atoms. Figure 8 shows the
dissociation energy necessary to remove one Ag atom (Figure
8a) and two Ag atoms (Figure 8b) from neutral Agn clusters.
In Figure 8a, one can see a first minimum at n = 9 for empty
cage Agn clusters with n = 7−18, that is, an easy dissociation of
Ag9 cluster with removal of one Ag atom, eq 1
Ag 9 + energy → Ag8 + Ag1 (1)
This indicates formation of stable Ag8 cluster with valence
electron configuration 1S2/1P6 (closed valence shell), con-
sistently with low polarizability of neutral Ag8 cluster in Figure Figure 8. Energy of dissociation of lowest-energy neutral clusters Ag4
5. through Ag22. (a) Loss of Ag1. (b) Loss of Ag2.

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Respectively, one can see in Figure 8b the first minimum at n
= 10, that is, dissociation of Ag10 cluster with removal of Ag2 by
eq 2:
Ag10 + energy → Ag8 + Ag 2 (2)
The minimum at n = 10 in Figure 8b indicates an easy
formation of stable Ag8 cluster, consistently with Figure 8a. For
larger clusters with one Ag in cage with n = 18−21, one can see
in Figure 8a the second minimum in the dissociation energy at
n = 21, which indicates formation of stable neutral Ag20 cluster
upon dissociation of Ag21 cluster. An enhanced stability of Ag20
cluster is also illustrated in Figure 8b, where a small energy is
needed for dissociation of neutral Ag22 cluster with formation of
Ag2 dimer and stable Ag20 cluster. Mass spectroscopic study of
neutral sodium clusters Nan has revealed that clusters with n =
8, 20, 40, 58, and 92 showed an enhanced stability.39 For
sodium clusters, magic numbers were explained in terms of a
one-electron shell model, when independent delocalized 3s
electrons of sodium atoms are bound in a spherically symmetric
potential well.39 For stable neutral Ag20 clusters, magic number
n = 20 would indicate that 5s electrons of Ag atoms contribute
to MOs of the cluster with formation of closed valence subshell
yielding electronic configuration 1S2/1P6/1D10/2S2.
Interestingly, there is local minimum in Figure 8a for
dissociation of Ag15 to stable Ag14 cluster with 14 valence
electrons and Ag1 monomer as well as the corresponding local
minimum in Figure 8b at n = 16 for dissociation of Ag16 to Ag2
dimer and stable Ag14 cluster. The Ag14 cluster has a closed
shell 1S21D102S2 configuration; Reber et al.21 found by DFT
computations an unusually low reactivity with molecular
oxygen for cationic Ag15+ cluster which is isoelectronic (by
the number of valence electrons) with neutral Ag14 cluster.
Further, global maximum in dissociation energy in Figure 8b at
n = 18 indicates highly stable Ag18 cluster, consistently with its
closed shell 1S2/1P6/1D10 configuration. Properties of lowest-
energy neutral, cationic and anionic Agn clusters originate from
their geometric and electronic structure. In the following
sections, we discuss computed electronic properties of cationic
Agn+ and anionic Agn− clusters.
3.3. DFT Computations of Cationic Silver Clusters
Ag2+ through Ag22+. Computed geometries of lowest-energy
cationic clusters from Ag2+ through Ag22+ are in Figures S11
and S12; they are close to those of lowest-energy neutral
clusters with cage structures dominating for n ≥ 7. Figure 9a
shows computed energy of dissociation of lowest-energy
cationic Agn+ clusters to Ag1 monomers and respective
Ag(n‑1)+ clusters.
In Figure 9a, one can see that loss of Ag1 monomer occurs
easier (i.e., with lower energy) for Agn+ clusters with even n,
compared to Agn+ with odd n in the whole range n = 4−22. Our
data in Figure 9a within n = 4−7 are consistent with Duanmu et
al.9 who reported that Ag1 is lost from small cationic Agn+
clusters (n = 2−7) with even n at lower dissociation energy
than for odd n. Moreover, our data in Figure 9a indicate that
the same “even/odd” trend continues for the larger Agn+
clusters within n = 7−22, where cage structure is of lowest
energy. Cationic Agn+ clusters with an odd n have an even
number (n − 1) of valence electrons and hence closed valence
shells, so that they are more stable than their counterparts with
even n.
For even n, one can see in Figure 9a the two minima at n =
10 and n = 16 for dissociation energy to Ag1 monomer. For the
first minimum at n = 10, cationic Ag10+ cluster is to be
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Figure 9. Energy of dissociation of lowest energy cationic clusters Ag4+
through Ag22+. (a) Loss of Ag1. (b) Loss of Ag2.
converted to stable Ag9+ cluster with eight valence electrons.
The predicted enhanced stability of Ag9+ cluster is due to
valence electron configuration of 1S2/1P6, consistently with an
enhanced stability of neutral Ag8 cluster in Figure 8a (high
dissociation energy). An enhanced stability of silver clusters
with eight valence electrons has been noted by Kahlal et al.40
who reported stable multiply charged [Ag13]5+ cluster of
octahedral geometry and its complexes with iron carbonyls as
found by the DFT calculations with BP86 functional. Relevant
experimental data were reported by Kruckenberg et al.41 who
used collision-induced dissociation (CID) in a Penning trap to
study low energy dissociation channels of cationic silver clusters
Agn+ with n = 3−20. They found41 dissociation of Ag10+ cluster
to Ag1 monomer and Ag9+ cluster but not to Ag2 dimer and
Ag8+ cluster, consistently with our data (Figure 9a) predicting
an enhanced stability of Ag9+ cluster with eight valence
electrons. For the second minimum at n = 16 in Figure 9a,
cationic Ag16+ cluster is predicted to be dissociated to Ag1 and
stable Ag15+ cluster with 14 valence electrons. Reber et al.21
predicted high stability of Ag15+ cluster by DFT with GGA
functional by Perdew, Burke, and Ernzenhof, consistently with
our data.
Computed dissociation energies of cationic Agn+ clusters with
formation of Ag2 dimer and Ag(n−2)+ clusters are shown in
Figure 9b. One can see that the minima in dissociation energy
correspond to odd values of n: at n = 5 (first minimum), at n =
11 (second minimum), and at n = 17 (third minimum). The
first minimum at n = 5 is due to an easy dissociation of Ag5+
cluster with four valence electrons to Ag2 dimer and stable Ag3+
cluster with two valence electrons. An enhanced stability of
obtained Ag3+ cluster is consistent with Duanmu et al.9 who
used DFT with M06 functional and predicted that when small
Ag3+, Ag5+, or Ag7+ clusters dissociate with formation of Ag2
dimer, their dissociation energies are 64.7, 39.7, and 57.0 kcal/
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mol, respectively. Namely, among small cationic Agn+ clusters Table 2. Experimental Data by the Low Energy CID for Loss
with odd n for n ≤ 7, dissociation of Ag5+ was predicted to of Ag1 Monomer and Ag2 Dimer from Agn+ Clusters with
require the lowest energy.9 Odd n (from Figures 2 and 3 in Refernce 41) versus Our
We also investigated the larger Agn+ clusters with 7 ≤ n ≤ 22. Computed Data
The second minimum in Figure 9b at n = 11 indicates an easy
loss of Ag1 by loss of Ag2 by our computed consistency of our
dissociation by eq 3 low energy low energy data in Figure computed data with
n CID in ref 41 CID in ref 41 10 experiment in ref 41
Ag11+ → Ag 2 + Ag 9+ (3) 9 detected detected loss of Ag1 yes
and Ag2
The obtained Ag9+ cluster is stable because it has the same
11 not detected detected preferred loss yes
closed shell configuration of eight valence electrons as stable of Ag2
neutral Ag8 cluster. Finally, the third minimum in Figure 9b at n 13 detected detected loss of Ag1 yes
= 17 indicates an easy dissociation by eq 4 and Ag2
15 detected detected loss of Ag1 yes
Ag17+ → Ag 2 + Ag15+ (4) and Ag2
17 detected detected preferred loss no for ref 41
The obtained Ag15+ cluster with 14 valence electrons is found of Ag2 yes for ref 21, 42,
stable in Figure 9b, consistently with the above discussion of and 43
second minimum in Figure 9a for Ag16+. 19 detected not detected preferred loss yes
It would be of interest to compare the preference of of Ag1
dissociation of Agn+ clusters with odd n (which are more stable
than the respective clusters with even n judged by loss of Ag1)
to Ag1 monomer versus Ag2 dimer. Figure 10 shows computed experimental data.42 In addition, anionic Ag13− cluster with the
same number of valence electrons as stable cationic Ag15+
cluster was also found to be highly stable.43 Such high stability
is apparently due to closed shell configuration 1S21D102S2 for
neutral Ag14, cationic Ag15+, and anionic Ag13− clusters.
3.4. DFT Computations of Anionic Silver Clusters Ag2−
through Ag22−. Computed geometries of lowest-energy
anionic clusters from Ag2− through Ag22− are in Figures S12
and S13. They are similar to lowest-energy neutral clusters:
linear or planar structures are at n = 2−5, empty cage structures
start from n = 6, cage with one Ag atom first appears at n = 18
and cage with two Ag atoms at n = 22. To our knowledge,
cohesion energy of anionic silver clusters Agn− was not
reported. We calculated Ecoh of anionic silver clusters Agn−
from computed cohesion energies of neutral Agn clusters using
eq 5
EA(neutral) − EA(Ag)
Ecoh(anion) = E coh(neutral) −
n
(5)
Figure 10. Dissociation energy and computed preferential loss of Ag1 where Ecoh (anion) is cohesion energy of Agn− anionic cluster,
monomer or Ag2 dimer for lowest-energy Agn+ clusters with odd n Ecoh (neutral) is cohesion energy of neutral Agn cluster, EA
within n = 5−21. (neutral) is electron affinity of neutral Agn cluster, and EA (Ag)
is electron affinity of Ag atom (numerically equal to 30.019
dissociation energy for loss of Ag1 monomer and Ag2 dimer for kcal/mol). Figure 11a shows calculated Ecoh of lowest-energy
Agn+ clusters with odd n within n = 5−21. Our computed data anionic Agn− clusters versus n in the range n = 2−22. In Figure
in Figure 10 for smaller cationic Agn+ clusters with n = 5 and n 11a, one can see a decreasing trend of Ecoh within n = 3−6
= 7 are in accordance with ref 9. In addition, we compared the when n increases, while Ecoh shows an increasing trend within n
preference of loss of Ag1 or Ag2 (based on lower dissociation = 9−22 when n increases.
energy) for larger cationic clusters for n = 9−21, see Figure 10 The increase in Ecoh versus n for larger clusters is likely due to
and Table 2. electronic properties of empty cage as lowest-energy structure
Table 2 shows analysis of experimental data by low energy at n > 7, while at n < 7 lowest-energy structures are planar or
CID of Agn+ clusters as in ref 41 versus our computed data linear. The maxima of E coh versus n correspond to
(Figure 10). One can see in Table 2 that fragmentation of Agn+ thermodynamically more stable anionic clusters. For cage
clusters with odd n to Ag1 monomer or Ag2 dimer as computed structures, the first maximum of Ecoh is at n = 7 for Ag7− cluster
by us using DFT with M06 functional has good consistency with eight valence electrons and 1S2/1P6 closed shell
with experimental data41 by the low energy CID, except for n = configuration, similarly to stable neutral Ag8 cluster (Figures
17. 5 and 8). For the second maximum in Ecoh at n = 17 in Figure
Our computed data indicate a preferential loss of Ag2 dimer 11a, anionic Ag17− cluster is predicted to be stable, due to the
from cationic Ag17+ cluster by eq 4 with formation of Ag15+ same closed shell configuration with 18 valence electrons as
cluster which is predicted to be stable. In accord with our stable neutral Ag18 cluster (see Figures 5 and 8). For charged
computations, the Ag15+ cluster was found to be of exception- aluminum clusters, electronic shell closing was found
ally high stability by DFT computations21 that are supported by responsible for an enhanced cohesion energy.44 Our data of
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The Journal of Physical Chemistry A
Figure 11. Energies of interactions of Ag atoms for lowest-energy
anionic clusters Ag2− through Ag22−. (a) Ecoh per atom. (b) BE.
enhanced stability of Agn− clusters with closed shell valence
electron configuration at n = 7 and n = 17 (Figure 11a) are
consistent with published data for charged aluminum clusters
and with our data for stable neutral Agn clusters with magic
numbers n = 8 and n = 18. Figure 11b shows calculated BE of
lowest-energy anionic Agn− clusters versus n. The same
observations are made as for Ecoh in Figure 11a. Namely, the
two maxima in Figure 11b for BE of Ag7− and Ag17− clusters are
consistent with closed shell electron configurations of stable
anionic clusters with 8 and 18 valence electrons, respectively.
Figure 12 shows the energy of dissociation of lowest-energy
anionic Agn− clusters to Ag1 monomer and smaller Ag(n‑1)−
cluster versus dissociation to Ag2 dimer and smaller Ag(n‑2)−
cluster. One can see that the following rules apply for n ≤ 11:
(a) for even n (n = 4, 6 and 10, except n = 8), the lower
dissociation energy is for loss of monomer Ag1 and (b) for odd
n (n = 5, 7, 9 and 11), the lower dissociation energy is for loss
of dimer Ag2. For small anionic Agn− clusters with n = 2−7, the
same observations were made by DFT with M06 functional.9
Preferred loss of Ag1 by small Agn− clusters with even n is
rationalized via formation of singlet state in the obtained
Ag(n‑1)− cluster. A preferred loss of Ag1 by anionic Agn− clusters
with even n within n = 2−7 was found experimentally45 by
energy-resolved collision induced dissociation (CID).
Preferred fragmentation of small anionic clusters Agn− with
odd n (even number of valence electrons) occurs with
formation of Ag2 dimer and Ag(n−2)− cluster with even number
of valence electrons forming singlet state. In attempt to resolve
the exception at n = 8 in Figure 12, we have tried all possible
geometries of anionic Ag7− cluster and could not find the one
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Figure 12. Energy of dissociation of lowest-energy anionic Agn−
clusters with formation of Ag1 monomer or Ag2 dimer and smaller
anionic clusters.
of lower energy than Ag7B- listed in Table S1 and used in
Figure 12. We believe that despite the above disagreement with
one experimental data point in ref 45 the DFT with M06
functional is reliable in computations of electronic properties of
neutral and charged silver clusters. We have also computed the
dissociation energies for larger Agn− clusters with n = 12−22,
and found that the above “even/odd” rule does not apply
(Figure 12). Namely, for n = 12−22 the dissociation requires
lower energy for fragmentation to monomer Ag1 than to dimer
Ag2 for each Agn− cluster. While this observation is intuitively
expected, experimental data are needed to confirm this finding.
It would be of interest to determine the validity of DFT with
M06 functional in computations of larger clusters with n > 22;
such investigations can be the topic of future work.
■
CONCLUSIONS
For neutral Agn clusters, transition from planar to empty cage
structure occurs at n = 7, from empty cage to cage with one Ag
atom at n = 18, and to cage with two Ag atoms at n = 22. For
the first time, medium-size neutral Agn, cationic Agn+, and
anionic Agn− clusters with n = 12−22 were systematically
studied by DFT with M06 functional via computed ionization
potential, electron affinity, polarizability, binding energy,
cohesion energy, and dissociation energy to Ag1 monomer
and Ag2 dimer. For medium-size neutral, cationic and anionic
silver clusters with n = 12−22, an enhanced stability is found
for the number of valence electrons 14, 18, or 20 per cluster.
Valence shell configurations of most stable neutral Agn clusters
are 1S2/1D10/2S2 for empty cage, 1S2/1P6/1D10 and 1S2/1P6/
1D10/2S2 for cage with one Ag atom. Preferential dissociation
of medium-size (n = 11−22) stable cationic Agn+ clusters with
odd n toward Ag2 dimer versus Ag1 monomer is predicted by
computations. Specifically, Ag11+ and Ag17+ clusters easily
dissociate to Ag2 and stable closed shell clusters Ag9+ and Ag15+,
consistently with published experimental data by collision-
induced dissociation (CID). Computed cohesion energy and
binding energy of anionic clusters Agn− with n = 2−22 are
mutually consistent and consistent with stable clusters with 8
and 18 valence electrons. For small anionic clusters Agn− with n
= 4−11, clusters with even n have the lower dissociation energy
for loss of Ag1 (except n = 8), while clusters with odd n have
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The Journal of Physical Chemistry A
the lower dissociation energy for loss of Ag2. For larger Agn−
clusters with n = 12−22, all clusters have the lower dissociation
energy for loss of Ag1 monomer.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpca.7b03905.
Figures S1−S14 and Tables S1 and S2 (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*Tel: +1-334-844-6985. E-mail: mckeeml@auburn.edu.
*Tel: +1-856-225-6282. E-mail: alexsam@camden.rutgers.edu.
ORCID
Alexander Samokhvalov: 0000-0002-7273-7322
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful for computer time provided by the
Alabama Supercomputer Center.
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