The pseudopotential panacea

Marvin L. Cohen

Citation: Phys. Today 32(7), 40 (1979); doi: 10.1063/1.2995618

View online: http://dx.doi.org/10.1063/1.2995618
View Table of Contents: http://www.physicstoday.org/resource/1/PHTOAD/v32/i7
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 The
pseudopotential
panacea
Webster's dictionary defines panacea as
a "remedy for all ills or difficulties; a
cure-all." A pseudopotential is an ap-
proximation to the real potential an
electron feels in a solid. In what sense
can it be called a cure-all? What are the
ills it cures, the difficulties it overcomes
or the problems it solves? And how does
it help solve problems? Our object here
will be to supply some answers to these
questions and to describe the growing
influence of theories involving pseudo-
potentials on solid state or condensed
matter physics.
In the last twenty years, the significant
success of solid-state theory in explaining
the detailed properties of real materials
is due to a large degree to the pseudopo-
tential approach.1 A partial list of ap-
plications would include: electronic
structure of solids and liquids, electron-
lattice interactions, superconductivity,
Marvin L. Cohen is professor of physics at the
University of California in Berkeley.
40 PHYSICS TODAY / JULY 1979
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surfaces and interfaces, chemisorption,
electronic transport, lattice vibrations,
bonding and crystal structure, and ap-
plications even beyond solid-state physics
(for example, molecular structure). The
predictive power of theories involving
pseudopotentials is very impressive. In
many cases where predictions from such
a theory have seemed to conflict with the
data, later experiments produced clear
agreement with the theory. Such suc-
cesses have given pseudopotentials the
aura of a panacea.
Nearly free electrons
A major conceptual problem of con-
densed-matter physics is the question of
why the nearly-free-electron model works.
The classical free-electron model used by
Paul Drude at the beginning of the cen-
tury explained many of the properties of
metals. With quantum extensions, in the
late 1920's, Felix Bloch and Arnold Som-
merfeld solved many of the remaining
"outstanding problems" (see PHYSICS
TODAY, December 1978, page 44). Here
the electrons are assumed to be nearly free
(a Fermi gas), but subject to an ad hoc
weak perturbing potential. In the 1950's
this model appeared to explain many de-
tailed properties of solid metals (for ex-
ample, their Fermi surfaces) and even
liquid metals.
However, there are two major reasons
why these successes were unexpected.
First, the kinetic energy of the conduction
electrons is about the same as their mu-
tual Coulomb energy. In sodium metal,
for example, the average distance between
conduction electrons is only 2 A, so that
the Coulomb energy is around 3.6 eV,
about the same as the kinetic energy.
The electrons should thus be strongly
correlated by their electrostatic interac-
tions. How can they then behave as
nearly free electrons? Second, the elec-
tron-ion interaction is expected to be on
the order of a Rydberg (~13 eV) in energy.
How then can the system behave as a gas
of nearly free electrons with the elec-
>-U))»U.JU ® IOf 0 iWncan Institute ol Physics
 Potentials for describing the behavior of valence electrons in solids
have considerably advanced our understanding of real materials, including
their optical spectra, bonding, superconductivity and surfaces.

Marvin L. Cohen

tron-ion interaction acting as a small
perturbation? These problems were then
probably as perplexing as quark confine-
ment and asymptotic freedom are in
particle physics today.
Quasiparticles and pseudopotentials
The absence of strong correlations has
its explanation in the Landau "quasi-
particle" picture or the theory of Fermi
liquids. The relative weakness of the
electron-ion interactions is explained by
the pseudopotential concept.2 Before
discussing these conclusions, let us ex-
plore two of the mental pictures used by
many solid-state theorists as their models
of microscopic behavior in a solid: the
standard model and the elementary-ex-
citation model.
In the standard model, the atomic cores
(nucleus plus electrons not involved in
bonding) form a periodic array; the va-
lence electrons in metals move throughout
the solid, behaving like free particles,
except for their weak interactions with the
cores. The "elementary" particles of the
standard model are cores and valence
electrons, the force is the Coulomb in-
teraction which is now treated dynami-
cally because of screening, and the tech-
nique for solving for the properties of the
system is ordinary quantum mechanics.
The difficult aspects of the problem are
the determination of the electron-core
potential, and the large number of degrees
of freedom: 10 2 ' particles in a typical
three-dimensional material.
In the elementary-excitation model the
solid is taken to be a "system responding
to probes." A probe such as electromag-
netic radiation, a magnetic field, or tem-
perature change excites the system and an
experimental measurement then deter-
mines the appropriate response function
such as the dielectric function, the mag-
netic susceptibility or the heat capacity.
In formulating a theory of the response
function, it is often most useful to com-
pute the responses of the system as if they
were caused by fictitious particles, the
"elementary excitations." These parti-
cles are called "quasi-particles" (usually
fermions) or "collective excitations"
(usually bosons). One of the best-known
examples of a type of quasi-particle is the
holes that are responsible for many of the
electrical properties of semiconductors.
Physically a hole is a vacant space in the
periodic electron structure of a crystal; it
moves like a positively charged particle
when electrons move to fill the vacant
spot, in turn leaving another vacancy.3
Another example arises when electrons
act collectively to produce long-wave-
length oscillations, as in a plasma. The
oscillations of the plasma can be quan-
tized and the collective excitations, or
"plasmons," can be pictured as being re-
sponsible for the responses of the system.
Other elementary excitations3 include
phonons, magnons, quasi-electrons, pol-
arons, excitons, Cooper pairs, rotons,
Bogoliubons, polaritons, and so on. Each
of these types of quasi-particles or col-
lective excitations exists (has been de-
fined) only to suit a particular system and
a particular probe. The interactions of
the elementary excitations are again dy-
namical Coulomb interactions, and the
technique for solving for the properties of
the system is essentially quantum elec-
trodynamics. Quantum electrodynamics
was introduced into physics for relativistic
problems where particles can be created
and destroyed, so it is also very useful for
the elementary-excitation model, where
the particles are fictitious and therefore
created and destroyed as the state of the
system changes.
The elementary-excitation model is

WAVE VECTOR q

s
-%EF

A typical real space pseudopotential (black) is weaker than the ionic or A typical reciprocal space pseudopotential. Values of V(q), for wave
all-electron potential (colored line) near the core region. The thin black vectors equal to the reciprocal lattice vectors, G, are indicated by the
line is a simple extrapolation for small r while the solid line extrapolation dots. For very small q the potential approaches (—2/3) times the Fermi
is more representative of most pseudopotentials. Figure 1 energy, which is the screened-ion limit for metals. Figure 2

PHYSICS TODAY / JULY

Downloaded 12 Nov 2012 to 152.14.136.96. Redistribution subject to AIP license or copyright; see http://www.physicstoday.org/about_us/terms 1979 41
modelled after the Landau picture of in-
teracting fermions. Landau showed that
the excitations of a system of strongly
interacting fermions were quasi-particles
resembling the free fermions making up
the system: The masses of the quasi-
electrons may differ from the free elec-
trons but the charge, spin, and statistics
are the same. So the excitations of the
electron system in sodium, for example,
can be described as a gas of free quasi-
electrons. This is the basis of the answer
to the puzzle of how supposedly highly
correlated electrons can act free.
What about the problematic weakness
of the electron-core or electron-ion in-
teractions? We have mentioned that
pseudopotentials provide an answer to
that question. Electrons in a solid or
dense liquid experience a potential made 1 2 3 4 5 6 7
up of two very different components. In
or near the cores they feel a strong atomic ENERGY E(eV)
potential, so they have wavefunctions that Reflectivity of silicon. The theoretical curve (color) was obtained using a pseudopotential calcu-
are very much like those of electrons lation.9 The experimental curve (black) is due to H. R. Philipp and H. Ehrenreich. Figure 3
bound in individual atoms. Between the
cores the electrons see an almost constant
potential, and the corresponding wave- time-independent Schrodinger equation in a crystal of cores and free electrons. It
functions are nearly plane waves. This thus provides us with a basis for explain-
schizophrenic behavior of the electrons ing why the nearly-free-electron model of
led Conyers Herring5 around 1940 to treat with a Hamiltonian, H, that is a sum of a Drude, Bloch and Sommerfeld works.
the wavefunctions of electrons that free-electron part, p'2/2m, and the core The remaining problem is to find the
propagate through the crystal as a linear potential, Vc. Using the values of 6C from pseudopotentials and elementary exci-
combination of core states and plane equation 2, we can write Schrodinger's tations that will serve as a basis for cal-
waves that he made orthogonal to the equation (after some algebraic manipu- culating the properties of a real sub-
filled core states. This "orthogonal- lation) as stance.
ized-plane-wave" approach produces a
wavefunction that has plane-wave char- Ec)<j>c (4>c\<t>) = E<f (3) Finding pseudopotentials
H<p + Z(E-
c
acter between the cores and resembles the Several methods have been used to
next excited atomic state near the cores. The sum over the core states represents construct pseudopotentials, including
These wavefunctions formed an excellent an operator acting on the smooth part of • Determination of potentials from
basis for calculations of response func- the wavefunction. We identify this op- models that mimic the form desired for an
tions and other properties. In the late erator with the repulsive potential analysis of equation 5. These models
1950's James C. Phillips and Leonard usually involve a few adjustable parame-
Kleinman 6 showed that one can derive VR4> = Y.(E-Ec)4>c(4>c\<t>) (4) ters, which are fitted to atomic data.
c
Herring's wavefunctions as solutions for • Forcing the pseudopotential to repro-
a problem in which a repulsive potential Schrodinger's equation thus becomes duce some measured properties of the
VR cancels much of the ion or core po- 1
(p2/2m + V)4> = EQ (5) solid. This potential can then be used to
tential V o producing a net weak pseudo- calculate other properties and analyze
potential. This pseudopotential provides where the potential V is the sum of the experimental data. This approach, which
the answer to the puzzle of how the sup- core potential Vc and the effective re- was developed by Phillips, David Brust,
posedly strong ion potentials can be re- pulsive potential VR. Franco Bassani and me is called the Em-
garded as weak. Note that the energy E in equation 5 is pirical Pseudopotential Method.
the exact energy of the state, so that we • Computing the pseudopotential di-
Phillips cancellation theorem can solve for eigenvalues using smooth rectly from information about atomic
The calculation of Phillips and Klein- wavefunctions via a plane-wave basis set structure, such as atomic spectra or
man provides a simple explanation of how and weak potentials. The repulsive po- atomic calculations. The part of the po-
a pseudopotential works, so we repeat it tential partially cancels the attractive core tential that arises from electron rear-
here. potential leaving a weak pseudopotential. rangement (as the atoms condense into a
Assume the real wavefunction \p has a This is the Phillips cancellation theorem. solid) can be calculated using the wave-
smooth part <p (the pseudo-wavefunction Morrel Cohen and Volker Heine later functions or charge density obtained from
that can be expanded in plane waves) showed that this conclusion is quite gen- solving Schrodinger's equation for the
plus a core part (which can be expanded eral and that the cancellation can be made condensed state. When the problem is
in core states, 4>c): almost complete in the core region. solved self-consistently, this is called
There are a few assumptions implicit in the Self-consistent Pseudopotential
bc4>c (1) this calculation. We use the standard Method.
model and assume the Born-Oppen- For many of the methods used, the
Following Herring's approach we make yp heimer approximation, which allows us to pseudopotential outside the core region
orthogonal to the core states and obtain picture the cores as stationary when dis- normally resembles the schematic curve
the coefficients bc from cussing the electron dynamics, and we shown in figure 1. Far from the nuclei, at
assume a Hartree or one-electron model large r, the potential behaves like an ionic
when we treat the potential Vc as an av- Coulomb potential. At smaller r the po-
The wavefunctions must satisfy the erage potential an electron feels anywhere tential deviates from the ionic one. The

42 PHYSICS TODAY / JULY

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 spectra for silicon. The energy positions
of the peaks are in excellent agreement;
peak heights are in fair agreement. The
peak heights are related to optical tran-
sition matrix elements and hence wave-
functions, which may not be as accurately
determined as the energy levels. We also
did not consider the effects of excitons, or
electron-hole bound states, which may
affect the accuracy of the calculations.
Although the spectrum does not appear
to be rich with structure, many energy
levels have to be consistent with experi-
ment for agreement on this level. The
success of these calculations is illustrated
more dramatically in modulated reflec-
tivity measurements, which, in essence,
determine the derivative of the spectrum.
Fine structure caused by optical transi-
tions is much more obvious here. Figure
ENERGY E(eV) 4 shows a comparison between experi-
mental results and a theoretical calcula-
Modulated reflectivity spectra reveal fine structure in optical spectra. The calculated pseudo-
potential results (color) are used to determine the origin of the observed structure. The experimental
tion for germanium. The calculation in-
results (black) are due to R. R. L. Zucca and Y. R. Shen. Figure 4 dicates that almost all the structure
shown can be interpreted in terms of op-
tical transitions.
change becomes large at about one-half a ciprocal lattice vectors are G = m2w/a, A wealth of uninterpreted data from
bond length (nearest-neighbor distance), where n and m are integers.) For the the 1960's and 70's has been analyzed with
where the repulsive force caused by the pseudopotential the Fourier expansion in such empirical pseudopotentials. These
orthogonality of the wave function to the terms of reciprocal lattice vectors is studies have explained the properties of
core-state wavefunctions becomes im- dozens of crystals and have resulted in
portant. (Typically, a bond length in a V(r) = Z V(G)S(G)eiG-r (6) general topological arguments for each
G
semiconductor is on the order of 2.5 structural class of solids; these in turn
A—for silicon it is 2.35 A). A good model The coefficients V(G) are called "form have given detailed predictions of optical
potential would consist of an ionic Cou- factors" of the potential; S(G) is the spectra. It was finally possible to cast
lomb potential cut off at around one-half "structure factor" that locates the atoms aside the old idea that, unlike atomic
of a bond length as shown by the hori- in the unit cell; it can be determined by spectra, the spectra of solids are too broad
zontal line in figure 1. A more accurate x-ray or neutron diffraction analysis. to be interpreted.
potential is given by the solid line. The Often V(q) is small at large q; so it is A host of other properties can be cal-
potential inside the core region is often only necessary to determine the form culated from the energy levels, wave
not well defined in many pseudopotential factors for a few reciprocal lattice vectors. functions and pseudopotentials deter-
schemes. Because we are normally only For example, for silicon the first G's have mined by these calculations, for ex-
interested in valence electrons outside the magnitude V3, V8, V11. With the three ample
core, this lack of information causes numbers V(V3), V(\'8) and V(v 11) one • the wave-vector and frequency-de-
few problems for valence electron energy can determine the electronic energy levels pendent dielectric functions
bands. One can also treat the core region or bands of silicon over a range of 1 Ryd- • lattice vibrations and electron energy
more exactly using "hard-core" pseudo- berg with an accuracy of about 1 or 2%. losses
potentials, as we discuss later. • temperature and pressure dependence,
It is convenient in dealing with periodic Electronic properties of energy levels
systems like crystals to work in "recipro- Let us now explore how to apply the • band gaps
cal space" whose points are wave vectors, Empirical Pseudopotential Method. We and many other spectral and transport
q, and to deal with the Fourier-analyzed first choose values for the three form properties.
potential V(q). At small q (or large r) the factors based on estimated or crude cal- One of the most interesting applica-
potential is attractive and looks like a culations. These are put into a pseudo- tions is to a study of the chemical bond in
screened Coulomb potential. For a metal potential Schrodinger equation, whose solids. By using the wavefunctions cal-
this implies that as q becomes small the solutions yield the energy eigenvalues and culated through the empirical pseudo-
potential should approach —2/3 of the corresponding wavefunctions. These potential we can obtain the electronic
Fermi energy. For larger q the potential eigenvalues and wavefunctions are then charge density as a function of position in
becomes positive because of the repulsive used to compute various response func- the crystal simply by squaring the wave-
nature of the core, and as q becomes very tions like the reflectivity or the density of function for each state and summing the
large the potential dies out. Figure 2 states. Comparison of the calculated and contributions of all the occupied states.
shows a typical potential, like those found the measured reflectivity, or the density Figure 5 shows the results for silicon. The
for many elements in the periodic table. of states and the energy distribution colored circles represent the cores, and the
Because of the periodic structure of curves from photoemission experiments contour lines indicate the charge density
crystals, Fourier transforms can be ex- reveals the accuracy of the form factors. for the valence electrons, which are de-
pressed as sums over reciprocal lattice We then adjust the V(G)'s until there is rived from the rearranged atomic 3s23p2
vectors, G, instead of integrals over all q. a good fit between the calculated and ex- electrons. The covalent nature of the
(The reciprocal lattice vectors determine perimental results. Once a fit is found Si-Si bond is clearly displayed by the
the Bragg scattering planes and are re- and the pseudopotential fixed, a host of "ball" or "ellipsoid" of charge located
lated to the symmetry of the crystal. In other properties can be calculated. between the cores. The experimental
a one-dimensional crystal with spacing a, Figure 3 contains a comparison of results given in figure 5 were derived from
the lattice vectors are R = na and the re- computed and measured reflectivity an analysis of x-ray data, in which the core

PHYSICS TODAY / JULY 1979

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The covalent bond of silicon is clearly displayed in this electronic charge-density-contour plot for
the valence electrons. The core electron contribution is represented by the large circles.
Agreement between theory9 (black) and experiment (color) is very good. The experimental deter-
mination (from x-ray analysis) is due to L. W. Yang and P. Coppens.
contributions to the charge density were
removed by subtracting calculated atomic
charge densities. Although there are
some uncertainties with respect to detail
in both the experimental and theoretical
results, the agreement between theory
and experiment is striking. The elec-
tronic charge density is concentrated in a
manner that was anticipated for the
crystal, but was never revealed before the
advent of pseudopotential calculations.7
Other covalent crystals have been exam-
ined and systems with partially covalent
and partially ionic bonding have also been
analyzed with this approach. By exam-
ining the contributions of individual
electronic states one can further reveal the
s, p, d bonding or antibonding nature of a
state with a straightforward picture.
Calculations based on pseudopotentials
and elementary excitations also permit us
to explore the interactions between the
electrons and the vibrating lattice. For
example, the electron-lattice or elec-
tron-phonon interaction is responsible for
binding pairs of electrons into Cooper
pairs. Using these interactions as a
mechanism, John Bardeen, Leon N.
Cooper and J. Robert Schrieffer devel-
oped one of the most successful theories
of physics, usually called the "BCS theo-
ry," which answers most of our questions
about superconductivity. To calculate
the superconducting transition temper-
ature, Tc, it is necessary to know the
strength of the electron-lattice interac-
tion, which in turn depends on the pseu-
dopotential. With current versions of the
BCS theory and modern computers, the
major stumbling block to accurate com-
putations of Tc is a knowledge of the
normal state properties of the supercon-
ductor. For simple metals, however,
transition temperatures derived from
44 PHYSICS TODAY / JULY 1979
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Figure 5
pseudopotentials compare very well with
experiment.
It is intriguing that pseudopotentials
derived from optical properties of semi-
conductors can be used to determine su-
perconductive properties of metals. For
example, analysis of the optical spectrum
of semiconducting indium antimonide
determines not only electronic structure
of InSb, but also the potentials for indium
and antimony individually. Some ex-
trapolation is necessary, but it is possible
to use the potentials derived from semi-
conductor data to analyze the electronic
structure and Fermi surface of indium
and antimony, and even to compute the
superconducting transition temperature
of indium.1 These results can be ob-
tained knowing only the lattice constants
and structure of In and Sb with no other
experimental measurements on these el-
ements.
In spite of this successful calculation,
one must be cautious in transferring
pseudopotentials from compound to
compound, because the electronic envi-
ronment may be very different in differ-
ent materials. For example, layer com-
pounds, metals, diamond-like semicon-
ductors, ionic insulators, and so forth, all
have their own peculiar electronic fea-
tures because valence electrons are ar-
ranged differently and are thus sensitive
to the pseudopotential in different regions
of r (or q) space. There are a number of
fortuitous cases like In, Sb and InSb,
where one can transfer the potentials di-
rectly, but there are many other cases,
such as crystal surfaces, where charge re-
arrangement is critical.
Surfaces and supercells
The surface of a crystal is not just the
end of a perfect crystal. Rather, the
atoms and charges rearrange themselves
considerably from the bulk material.
Furthermore, a surface, like a defect
within the bulk of the crystal, breaks the
fundamental periodicity. Localized
configurations—like atoms, molecules,
defects, and surfaces—present real
problems for calculations that depend on
crystal periodicity. One solution, used by
Joel Appelbaum and Donald Hamann, is
to match bulk pseudopotential solutions
to surface-state-like solutions. Another
approach is to retain our precious peri-
odicity by introducing the concept of
"supercells."
A supercell is simply a large "unit" cell
of a crystal that can contain many lattice
sites of an ordinary crystal. The struc-
ture factor, S(G), of equation 6 accounts
for the positions of the atomic cores, and
we can use it to describe supercells with
any arrangement of atoms we like. If, for
example, we wish to study an atom or a
molecule we can use the structure factor
to create a large cell with the atom or
molecule in the center of the cell and
empty sites or space in the rest of the cell.
This supercell can then be repeated infi-
nitely and the problem to solve is of the
same type as before, but with a large unit
cell; the empty space ensures that there
will be little interaction between the
atoms or molecules. If we wish to study
surfaces we can use a supercell that has
the regular crystal periodicity in the x-
and y-directions, but has slabs of finite
thickness with space between them in the
2-direction; the "crystal" consists of an
infinite number of slabs of material
stacked in the 2-direction, with space to
isolate them. The new geometry retains
the periodicity we found useful earlier,
but the much larger unit cell also intro-
duces new reciprocal lattice vectors, G,
and forces us to extrapolate the V(q)
curves.
The pseudopotentials needed to study
surfaces have two parts: the ionic (or
core) contribution, which is essentially the
same in the atom or the bulk as it is at the
surface, and the electronic contribution,
which depends on the electronic arJ
rangement. One can estimate the elec-
tronic part of the potential fairly accu-
rately from the charge density, using the
density-functional approach which allows
the determination of the Hartree and
exchange-correlation potentials directly
from the electronic charge density. To
begin the calculation, we use an empirical
pseudopotential to compute the charge
density, fr6m which, in turn, we calculate
the electronic contribution to the poten
tial. We then add the ionic potential and
structure and use the new potential to
begin the calculation over again. Onc<
the input and output potentials are th<
same, that is, once the calculation is self
consistent, the problem is considere<
solved. For a surface, for example, durinj
the first few iterations, electronic charg-
begins to escape from the bulk into th
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 vacuum, but then the resulting change in
the potential acts to pull it back; at self-
consistency a compromise is achieved.
Several localized configurations have been
analyzed using the above method; they
include diatomic molecules, surfaces,
steps on surfaces, adsorbates and vacan-
cies.
The (111) surface of silicon has been
one of the most studied8 surfaces during
the recent renaissance in surface physics,
and it provides a good example of what
the self-consistent method can achieve.
Figure 6 shows a ball-and-stick com-
puter-drawn model of a silicon crystal
near its (111) surface. Because of the
surface, the topmost silicon atoms have
only three nearest neighbors whereas bulk
silicon atoms have four. How do these
"cut" or "dangling" bonds rearrange once
they are cut—do they dangle like cut
rop^es, pull back, or smooth out? Another
important question concerns the exis-
tence, suggested by Igor Tamm in the
early 1930's, of surface states, which are
electronic states localized near the surface
that decay both into the vacuum and into
the bulk solid. A further point of interest
is how far the perturbations caused by the
surface extend back into the bulk region
of the solid.
A charge-density plot for the surface
can answer some of the questions. One
expects that such a plot would be similar
to figure 5 for the bulk, but with differ-
ences arising from the charge redistribu-
tion at the surface. The cover of this
issue of PHYSICS TODAY shows the total
electronic charge density near the Si (111)
surface. The results resemble the ball-
and-stick model of figure 6. However,
A ball-and-stick model of the silicon (111) surface reveals the "dangling bonds" on the outermost
atoms. The colored balls represent the cores that are used to display the charge-density config-
urations on the cover and in figure 7. (From reference 8.)
46 PHYSICS TODAY/JULY 1979
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they also reveal that the dangling bond
does not "dangle;" the surface "heals," in
that the charge readjusts and smooths
out, explicitly showing that the surface is
not just the end of a bulk crystal. The
figure also demonstrates that the per-
turbation of the surface affects the total
charge only a few layers into the crystal.
Near the surface there are evident chan-
nels in the total charge density, and it is
likely that impurities can migrate into the
crystal through these channels.
As for surface states, these would not
show up in the total charge density unless
they had amplitudes comparable with
bulk states. It is possible to search for
these states by comparing the electronic
states (using a density-of-states function)
at the surface layer with those of the bulk.
The analysis is straightforward and shows
that there is indeed a prominent surface
state, whose energy lies in the forbidden
semiconductor gap region. This state has
been called the "dangling bond" surface
state, because it is believed to be associ-
ated with the cut (111) bond. The
charge-density contour plot for this state
appears in figure 7, which shows that it is
a bona-fide surface state, spreading into
both the vacuum and the bulk, while
being localized close to the outermost
atom on the Si(lll) surface. Experi-
mentalists have explored the properties
of this state with photoemission and
electron energy-loss techniques and
theorists have analyzed it with self-con-
sistent potentials using both supercells
and the matching approach of Appel-
baum and Hamann.
Other surface states are localized in the
second or third layer—the so-called "back-
Figure 6
bond" states. Furthermore, some sur-
faces exhibit more complex geometries.
For example, we used an idealized model
for the Si (111) surface in that we assumed
the geometry of the bulk extended to the
surface. However, it is believed that the
atoms on the surface "reconstruct," that
is, form an array different from the ideal
shown in figure 6. Low-energy electron
diffraction (LEED) studies on Si(lll)
indicate that one likely reconstruction is
a "buckled" surface. The topmost atoms
in figure 6 rearrange so that one atom
pushes out along the (111) direction while
the next one pulls in. This creates a so-
called (2 X 1) surface. Applying the
self-consistent procedure to this case re-
veals that the dangling-bond surface state
associated with the "in" atom loses its
electron to the "out" atom. It is even
possible to calculate the optical spectrum
for electron transitions from states asso-
ciated with "out" atoms to states of "in"
atoms.
Other semiconductor, insulator, sim-
ple-metal and even transition-metal sur-
faces have been explored using the self-
consistent method. Even metal-semi-
conductor interfaces (Schottky barriers)
and semiconductor-semiconductor in-
terfaces (heterojunctions) have been an-
alyzed in detail. Steps on surfaces, bulk
vacancies and adsorbates, such as hy-
drogen or chlorine on silicon or hydrogen
on molybdenum or palladium, have also
been studied. The applications in this
area have only just begun.
Other new developments
While many recent applications of
pseudopotentials have been in surface and
interface research, progress in bulk cal-
culations and recent work on the con-
struction of basic theory and further ap-
plication of pseudopotentials have been
considerable. A major effort has gone
into calculations for complex systems.
Layer and chain compounds, complex
polytypes of simple materials like silicon
or germanium that simulate amorphous
systems, materials with d-electrons, and
complicated crystal structures are sam-
ples of the effort in this area. A good ex-
ample of the last item is the high-tem-
perature superconductor NbaGe. Pseu-
dopotentials have permitted not only the
computation of the complicated energy
bands and densities of states, but also the
analysis of the charge density. This anal-
ysis illustrates how charge is distrib-
uted among niobium, germanium and
the region between these atoms. The
dominant effect is that charge leaves both
Nb and Ge atoms to fill the space between
them, yielding a "metallic" configuration
for the charge density. One hopes that
calculations of this kind will supply useful
information for understanding why the
superconducting transition is at a high
temperature in this material.
In all of the calculations described here
it was first necessary to know the struc-

The dangling-bond surface state associated
with the Si (111) surface. The charge density
for this localized state decreases rapidly into the
vacuum and bulk solid. This state has been
observed experimentally. Figure 7
ture of the system considered, that is, the
bulk crystal structure or the surface
atomic arrangement. Often, as in the
case of surfaces, this arrangement is dif-
ficult to determine. If the pseudopo-
tential could be used directly to calculate
total energies, minimizing the energy with
respect to atomic configuration would
yield a direct determination of the crystal
and surface structure. This has been a
difficult area; success has only recently
been achieved for some bulk solids, and
only partial success is achieved for the
silicon surface . The reason for the diffi-
culty is that the energy differences to be
calculated are very small, and extremely
accurate pseudopotentials are needed.
As we have seen, one does not need
detailed knowledge of the pseudopoten-
tial in the core region to expose most of
the physics involved in problems of elec-
tronic structure calculations. However,
for crystal-structure analysis, for deter-
mination of the conditions for alloy for-
mation, for detailed molecular studies in
the core region and for other problems,
one must treat the region close to the
atomic core with care.
To examine the core region, Gary Si-
mons and Aaron N. Bloch have intro-
duced an analytic form of the pseudopo-
tential that contains a repulsive 1/r2 term.
This term would cause the pseudopoten-
tial curve in figure 1 to pass through zero
and become positive for small r. Because
of the strong repulsive force near r = 0
these potentials are often called "hard-
core" potentials. The zero of the poten-
tial can be identified with the core radius.
Phillips and James R. Chelikowsky used
this approach to refine the semi-phe-
nomenological theory of A. R. Miedema
on alloy formation. This research has
opened up new vistas both for pseudo-
potential development and for the theory
of metallic alloy formation. Wanda An-
dreoni, Alfonso Baldereschi, F. Meloni
Downloaded 12 Nov 2012 to 152.14.136.96. Redistribution subject to AIP license or copyright; see http://www.physicstoday.org/about_us/terms
and Phillips have expanded on the Si-
mons-Bloch approach and developed
more flexible analytic forms for the
A closer look..
pseudopotential. Alex Zunger and I have
explored another avenue which we call the
"first-principles pseudopotential ap-
proach" (almost contradictory terms). In
this scheme, the pseudopotential is ob-
tained directly from atomic wave func-
tions without empirical fitting. These
pseudopotentials have the proper be-
havior near the core as well as giving ac-
curate results in the atomic and molecular
limits. First-principles pseudopotentials
also give the Simons-Bloch results for
quantities such as the core radii. While
the hard-core pseudopotentials are useful
for a large class of problems they also have
a disadvantage in that the potential is
...at
large within the core, so that the compu-
tations require a more sophisticated basis
EG&G
set than plane waves for the wavefunc-
tions and hence large computer facili-
Lock-Ins
ties. tells the
In many calculations, the old "soft-
core" pseudopotentials are being replaced real story...
by a variety of "hard-core" pseudopo-
tentials. Although the hard-core poten-
tials can be more difficult to manage, they
are often more accurately determined,
especially in the core region. So the
pseudopotential domain is now being
expanded to include phenomena that Take dynamic reserve for instance...
depend on electronic structure near the the instrument's ability to handle
core region—a region which at the outset noise...the Model 186A allows a
was forbidden. But shouldn't we expect signal to be measured in the presence
this from a true panacea? of up to 300.000 times full scale
noise. NO competitive instrument
comes close to this performance. And
frequency range...0.5 Hz to 100
This article is based in part on a talk given at kHz...is packed into every
the meeting of The American Physical Society instrument...not into boxes of color-
on 20 March 1979 in acceptance of the 1979 coded boards to be changed! And
Oliver E. Buckley Prize in Solid State Physics. you don't have to give up 100
The author wishes to acknowledge support nanovolt sensitivity...or time constant
from the National Science Foundation; the or zero offset when you change
Division of Materials Sciences, Office of Basil-
dynamic reserve...once you set
Energy Sciences, US Department of Energy, it...you get it!!!! No wonder EG&G
and a Guggenheim Foundation Fellowship. Lock-In Amplifiers are the instruments
He also wishes to thank the department of more researchers select for critical ex-
physics at the University of Hawaii, Honolulu, periments. Shouldn't you take a
for their hospitality while much of this article closer look?
was written.
Other points you'll see on closer
References inspection of EG&G Lock-Ins...
1. A review of pseudopotential research is • True differential, floating or
given in: M. L. Cohen, V. Heine, Solid grounded inputs
State Physics 24, 37 (1970), as well as in • Full programmability
references 2, 3 and 4. • True 10-turn phase & zero offset
2. W. A. Harrison, Pseudopotentials in the controls
Theory of Metals, Benjamin, New York • Full frequency range narrow band
tracking
(1966)".
• Card-free, alignment-free fre- 1
3. C. Kittel, Introduction to Solid State quency changing
Physics, 5th ed., Wiley, New York (1976).
4. J. C. Phillips, Bonds and Bands in Semi- For more information on EG&G
conductors, Academic, New York (1973). Lock-Ins, write or call today.
5. C. Herring, Phys. Rev. 57, 1169 (1940). EG&G PRINCETON APPLIED
6. J. C.Phillips, L.Kleinman, Phys. Rev. 116, RESEARCH, P. O. Box 2565,
287 (1959). Princeton, NJ 08540;
Phone: 609/452-2111.
7. M. L. Cohen, Science 179, 1189 (1973).
8. M. Schluter, J. R. Chelikowsky, S. G. Louie,
M. L. Cohen, Phys. Rev. B12, 4200 (1975). PRINCETON APPLIED RESEARCH
9. J. R. Chelikowsky, M. L. Cohen, Phys. Rev.
B14,556(1976). n
Circle No. 22 on Reader Service Card
PHYSICS TODAY / JULY 1979
47