J. Phys. Chem.
1987, 91, 3141-3149 3141
FEATURE ARTICLE
Physics of Metal Clusters
Marvin L. Cohen,*
Department of Physics, University of California, and Materials and Molecular Research Division, Lawrence
Berkeley Laboratory, Berkeley, California 94720
M. Y. Chou,
Corporate Research Science Laboratories, Exxon Research and Engineering Company, Annandale,
New Jersey 08801
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W. D. Knight, and Walt A. de Heer
Department of Physics, University of California, Berkeley, California 94720 (Received: October 13, 1986;
In Final Form: February 20, 1987)
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The theoretical and experimental basis for some current physical models are described and applied to explain the properties
of clusters of a few prototype s-p metals. Emphasis is given to the successful use of models such as jellium which were originally
developed for bulk solids. It is shown that the experimental data and the results of the jellium model point to a shell model
description of metal clusters.
Introduction
Metal clusters have attracted increased attention recently in
both the physics and chemistry communities. Experimental
techniques have become more sophisticated and flexible so that
reproducible data can be used to distinguish between competing
models and theories. On the theoretical side, physicists and
chemists have been able to apply methods developed for other
systems to explore the structural and electronic properties of
clusters. Because clusters lie somewhere between molecules and
surfaces in the hierarchy of atoms to molecules to solid surfaces
to bulk solids, approaches and models to study them have come
from both sides. In most cases, condensed matter theorists have
applied solid-state models while quantum chemists have moved
from calculations on complex molecules to clusters. Experi-
mentalists have also witnessed a synthesis of approaches from
physics and chemistry. The objectives of those working in the
two sciences often differ considerably, and language problems have
developed. Part of the motivation for the discussion here is to
clarify some of the models used in the more physics-oriented
approaches. A recent review by the authors1 contains more de-
tailed information and more references.
The focus of this review is on clusters of simple metals (without
conduction d-electrons). We will describe a method which treats
each metal cluster as a structureless ionic jelly permeated by
itinerant electrons. This jellium model has had considerable
success in explaining many properties of bulk simple metals and
the approximations involved are well understood. When the crystal
structure is eliminated, the quantum energy levels for the valence
electrons are determined by the confining region. For solids and
clusters, the constraints of the region can, for example, be modeled
with a macroscopic box or a microscopic spheroid, respectively.
In both cases, the valence electrons are no longer identified with
specific atoms but are part of a sea of indistinguishable electrons
with each experiencing the effects of the positive background, the
average potential of the other electrons, and the constraints of
the confining region.
(1) de Heer, W. A.; Knight, W. D.; Chou, M. Y.; Cohen, M. L. Solid
State Phys., in press.
0022-3654/87/2091 -3141 $01.50/0
This model for a cluster has many features in common with
modern models of nuclei. Unlike the model of an atom where
the Coulomb interaction dictates that the principal and orbital
angular momentum quantum numbers n and l obey the rule l <
n, a spherical or spheroidal cluster model implies that the total
resultant potential of the cluster is not Coulombic in form and
/ is not restricted. In fact, a lowest order approximation is to
consider a square-well, harmonic oscillator, or hybrid potential
(Figure 1) as is done for nuclei.
To justify this model and explain its construction, we begin by
examining the bulk solid. This is where the approximations and
applications were first tested. Next, we make the extension to
clusters and explore the main consequences of the model which
include the existence of shell structure. The experimental results
are then described followed by discussions of the comparisons
between experiment and theory.
Theoretical Models
Model of a Bulk Metal. The one-electron model has been very
successful in describing a wide variety of solid-state properties.
In this model, an electron in a solid is viewed as interacting with
a periodic potential consiting of contributions from the ions and
an average interaction from the other electrons. The total elec-
tronic energy of this system is then the sum of the energies of the
individual electrons.
To calculate the individual electron energies, it is necessary to
provide a model for the crystal. Several successful approaches
are available. Here we focus on the pseudopotential approach
and later view jellium with its smeared out positive background
as a special case of the pseudopotential model where the solid is
assumed to consist of a periodic array of positive cores or ions
and a sea of itinerant valence electrons. A core consists of a
nucleus plus its core electrons, and it is considered to be the same
in the solid as it is in an isolated atom. For example, sodium is
described as a bcc array of cores immersed in a free-electron gas
of valence electrons. The cores each contain a nucleus and the
10 core electrons [(ls)2 *(2s)2(2p)6]. Each sodium core has a net
single positive charge, and the (3s)1 valence electrons are no longer
associated with a specific core but are shared among the cores.
&copy; 1987 American Chemical Society
3142 The Journal of Physical Chemistry, Vol. 91, No. 12, 1987
Figure 1. Energy-level occupations for three-dimensional harmonic os-
cillator, intermediate, and square potential wells.
Figure 2. A schematic pseudopotential (solid line) showing the reduction
of the attractive Coulombic ion potential (dashed line) in the core region.
The total energy of the system consists of the kinetic energies
of the cores and electrons and the electrostatic potential energies
arising from core-core, electron-core, and electron-electron in-
teractions. Since the core separations are large compared to their
sizes, the interactions between the cores are Coulombic and can
be evaluated by using standard Madelung summations.2 In the
approach described here, electron-core interactions are evaluated
via a pseudopotential,3 and electron-electron contributions are
approximated by a local density approximation4 described below.
The electron-core pseudopotential contains both the attractive
Coulomb interaction of the positive core and a repulsive potential
which is constructed to reproduce the effect of the Pauli exclusion
principle between the valence and core electrons. The latter term
tends to force the valence electrons out of the core region where
it cancels much of the attractive Coulomb potential. A schematic
picture of a pseudopotential appears in Figure 2. Because of the
cancellation in the core region, the effective potential is weak. In
addition, there is electronic screening of the core potential which
further reduces the interaction of each of the electrons with the
cores.
The last of the three potential energy terms arises from elec-
tron-electron interactions. This term is usually divided into
(2) Kittel, C. Introduction to Solid State Physics, 6th ed.; Wiley: New
York, 1986.
(3) Cohen, M. L.; Heine, V. Solid State Phys. 1970, 24, 37.
(4) Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1333.
Cohen et al.
Coulomb, exchange, and correlation interactions among the va-
lence electrons. Each can be evaluated by using potentials which
depend only on the charge density. This is the local density
approximation (LDA) since the potentials based on this ap-
proximation are local in space; that is, the potential at position
r for exchange and correlation is a functional of the electron density
at point r. These contributions to the energy will be computed
explicitly later within the jellium approximation.
Both the pseudopotential and LDA methods have become
standard theoretical tools3-5 in the physics of solids and molecules.
Together they provide a method for determining the structural
and electronic properties of solids. The approach to structure
determination involves the computation of the total energy of a
solid for varying structural arrangements. The minimum energy
structure (for a given volume fixed by the applied pressure) among
likely candidates is the preferred choice. Unfortunately, not all
structures can be tested, but considerable success has been achieved
in predicting high-pressure structures5* by using less than a dozen
candidate structures. For a given structure, many structural and
electronic properties can be determined theoretically.5*’6 These
include lattice constants, bulk moduli, cohesive energies, phonon
spectra, structural phase transitions, superconductivity, and other
solid-state properties. The successes of this approach for extended
systems motivate the use of similar schemes for clusters.
The above model has been applied directly to clusters of atoms,
but when these ab initio methods are used they become compu-
tationally complex for large clusters. Hence, as a first step, the
jellium model can be used. This model has had wide application
in solid-state physics for bulk and surface6 properties of solids.
The approach is similar in principle for computing the electronic
energies for clusters.’’7'8 For the bulk, the solid is viewed in the
same way as it is in the pseudopotential model, but the discreteness
of the cores is eliminated by smearing out the positive charge into
a uniform structureless background “jelly". In the jellium or
homogeneous electron gas model, the positive background charge
density ep0+ is cancelled by a similar electronic contribution -ep0
to assure charge neutrality. Here the average density of the
electrons is used
Po
=
N/n (1)
when N is the total number of electrons and 12 is the volume.
When constructing the total energy £T of this jellium system, the
average electrostatic electronic energy is left out since this is
cancelled by the Coulomb interaction of the uniform positive
background with itself and the Coulomb interaction of the uniform
positive background with the electrons. Now £T = NEC where
£e is the ground-state energy of each individual electron.
A parameter r, is used to characterize the density of the electron
gas; r, is the radius per electron measured in Bohr radii a0
7*-(r,a0)3 = —
(2)
3
Po
The various energies of the electron gas can now be expressed in
terms of rv In rydbergs, the Fermi energy2 £F = 3.6832/rs2 and
the average kinetic energy per electron of an electron gas2 is £KE
=
3/5£f or
£ke =
2.2099/r,2 (3)
The direct Coulomb interaction between electrons is omitted as
described above, but an exchange interaction remains. Because
of the Pauli principle, two electrons cannot have all their quantum
numbers alike. Antiparallel spin electrons differ in their spin
quantum number, but parallel spin electrons do not and hence
avoid each other in an effort to satisfy Pauli’s rule. Because of
(5) (a) Cohen, M. L. Science 1986, 234, 549. (b) Cohen, M. L. Phys. Scr.
1982. Tl, 5.
(6) Lang, N, D. Solid State Phys. 1973, 28, 225.
(7) Martins, J. L.; Buttet, J.; Car, R. Phys. Rev. B 1985, 31, 1804.
(8) Knight, W. D.; Clemenger, K.; de Heer, W. A.; Saunders, W. A.;
Chou, M. Y.; Cohen, M. L. Phys. Rev. Lett. 1984, 52, 2141.
Feature Article
the charge on the electron, this repulsion changes the Coulomb
energy of the system. Within the jellium model, the exchange
energy
Ex =
-0.9163/r, (4)
Higher order correlations beyond exchange give rise to terms in
power of rs°, In (rs), r„ etc. The first terms in the correlation energy
Ec are
Ec = -0.094 + 0.0622 In (rs) (5)
So for bulk jellium
2.2099 0.9163
--
0.094 + 0.0622 In {rf (6)
and this value is accurate as rs —*• 0 which is the high-density limit.
In the above model, the volume is assumed to become very large
and surfaces are neglected. When surface effects are included,6
the electron gas is not terminated at the edge of the jellium but
rather it spills out. This effect changes the potential, and the
calculation must be done self-consistently; that is, the potential
producing the electronic charge density depends on the spatial
form of the density which in turn acts back on the potential.
Self-consistent jellium models for surfaces give excellent insight
into the surface properties of real metals. Since the approximations
used are only appropriate for ground-state energies, excitations
involving electron removal are not determined accurately. Work
functions are within 10-20% of experimental values, but it is not
clear whether the discrepancy arises from the elimination of crystal
structure or from the approximations used for exchange and
correlation in this “ground-state” model.
In general, the jellium model for bulk solids is expected to be
a good approximation when the electron-core interactions given
by the pseudopotential are a small perturbation on the energy.
For crystals like diamond, silicon, or NaCl, the pseudopotentials
are relatively large and the charge density is not uniform. Covalent
bonds pile up charge, and ionic potentials transfer electrons. For
metals like Na and other alkalis, the pseudopotentials are small,
and the charge density is quite uniform. Covalentlike contributions
giving directional bonding do not appear. These systems are ideal
cases for using the jellium and free-electron approaches and ap-
plications have become standard textbook examples.2
Jellium Model for Clusters. The preferred approach for
computing properties of clusters would be to use ab initio tech-
niques like the total energy pseudopotential approach. However,
since the structure of the cluster is unknown, the positions of the
atoms must be determined by a minimum energy principle as
described above for solids. This approach would require repeated
calculations7 each time an atom is moved and hence can be done
for only small clusters for a predetermined structure or for more
simplified theoretical models.
For clusters of silicon, the energy associated with the positions
of the atoms is critical in determining the covalent bonds and the
large contribution to the energy coming from the pile-up of charge.
Hence, for this case, an accurate model of the electron-core
potential is necessary. For rare-gas clusters, the interactions are
weak, and there is little charge rearrangement. The total energy
depends on packing; therefore, structure is again critical. However,
in the case of simple metal clusters, one argues that structure is
not critical and the pseudopotential is weak; hence, the use of a
jellium model is appropriate. Another post hoc argument for the
applicability of jellium for clusters is that the structural energy
has a small variation as a function of cluster size. Since this is
not the case for the electronic contribution, the latter is dominant
in determining the relative stabilities of clusters. This aspect will
be discussed later.
Because of the simplicity of the jellium background potential,
it can be applied to clusters of arbitrary size. The cluster density
is fixed by using the rs value of the bulk solid. Cluster sizes for
the model are determined by the number of atoms in the cluster.
Hence, the jellium calculation for clusters has some of the features
of the self-consistent surface calculation for solids described above.
The effects of charge rearrangement have to be considered.
The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 3143
A simpler non-self-consistent approximation is to confine the
electrons in a spherical box with infinite potential walls. This
would not allow for the “spilling out” of the charge at the surface,
but this approximation does illustrate the overall nature of a
free-electron gas confined to a sphere. The energy eigenstates
are also eigenstates of angular momentum, and shell structure
imposed by the potential is evident (Figure 1). A next possible
approximation to account for the surface effects is to use a finite
square well with rounded corners. This model also yields shell
structure (Figure 1); its detailed properties depend on the pa-
rameters used to describe the potential.
The approximate models give a reasonably accurate picture of
the energy levels and the occurrence of degenerate states arising
from the spherical symmetry. When a fully self-consistent jellium
model calculation is used, the results do not change much from
the well models. Again, degeneracies and shells are apparent.
When the total energy of the system is considered, the special
stability associated with completed shells becomes manifest.
The principal success of the jellium model for clusters is that
it accounts for the steps in the total electronic energy as a function
of the number of atoms N. These steps are a direct consequence
of the spherical symmetry leading to degenerate electronic energy
levels and shells which resemble the energy-level structures of
nuclei and atoms. Stable alkali metal clusters are predicted and
observed for N = 2, 8, 18, 20, 40, 58, and 92, which represent
the closed-shell spherical clusters. Further fine structure in the
abundance spectra is predicted9 for the open-shell clusters by
allowing for ellipsoidal deformations corresponding to observed
subshell closing at, for example, N = 26, 30, 34, 36, 38, etc.
Analogous distortions were predicted and observed in nuclei ac-
cording to the Nilsson model. Discussion of other refinements
and limitations of the jellium model and the LDA will be presented
in the section on theoretical results.
Ellipsoidal Distortions. The Jahn-Teller theorem states that
a molecule in a symmetrical configuration with both vibrational
and non-Kramers electronic degeneracies is unstable against
distortions which lower the energy. Analogous distortions occur
for both atomic nuclei and.metal clusters. Detailed calculation9
has shown that most open-shell clusters which are allowed to distort
at constant volume assume minimum energy ellipsoidal shapes.
For x = y ^ z with respective major axes b and a, the distortion
parameter is given by
2{a -
b)
=
V (7)
a + b
which can have values up to 77 = 0.5 for open-shell alkali clusters
N < 100. A fully self-consistent treatment for ellipsoidal clusters
has not yet appeared. However, the simplified models which are
known to work for spherical clusters can be applied. A modified
three-dimensional harmonic oscillator potential may be used to
derive the energy levels for a spheroidal cluster. It may be inferred
from Figure 1 that a “squared” harmonic oscillator potential closely
resembles a “rounded” square well, and the dynamical degeneracies
inherent in the harmonic oscillator are similarly broken as when
the Id level splits and drops below the 2s level in Figure 1. It
may also be seen that the spheroidal harmonic oscillator has two
characteristic frequencies. For the prolate ellipsoid the curvature
of the potential is the smaller and the frequency lower along the
major axis. The difference frequency is a measure of the energy
splitting which is characteristic of the distortion parameter 77. The
scaling factor for the oscillator frequencies is the spherical fre-
quency9
w0
~
EfN~l/3 (8)
where EF is the Fermi energy, for example, 2.7 eV for sodium.
The similarities among the several “well” models are clear
enough, the utility of the intermediate rounded or squared well
for dealing with spherical clusters is well established, and it should
be applicable to both the spheroidal frequencies wxo, and ux which
(9) Clemenger, K. Phys. Rev. B 1986, 86, 619; see also ref 66.
3144 The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 Cohen et al.

characterize an open-shell cluster. If cluster distortions are

constrained to occur at constant volume, the frequency coz is
associated with the symmetry axis, the transverse frequency wxy
is weighted doubly, and the frequencies are related by9

=
^x,y^z "03 (9)

The main first-order effects will depend on symmetry, and these

are observed, for example, as fine structure in the mass abundance
spectra corresponding to increments of N + 2 (clusters 35-36 and
37-38) or N+ 4 (clusters 27-30, 31-34). The first corresponds
to the fact that the spin degeneracies persist in the spheroids. The
second results from the axial symmetry.
It is easily shown that the energy levels of the ellipsoidal model9
correspond with experimental abundance spectra and naturally
include the results of spherical shell theory. In the Clemenger-
Nilsson model9 the total electronic energy for a cluster is found
by summing the individual electron energies, using the harmonic
oscillator frequency co0 as a scaling factor. The Nilsson Ham-
iltonian includes an anharmonic term which squares the well as
discussed above and a spin-orbit coupling term which is needed
to describe nucleon interactions but which is omitted for alkali
clusters whose spin-orbit effects turn out to be smaller than any
other energy splittings in the problem. The total electronic energy
is calculated for all N electrons in a cluster and is a function of
the distortion factor rj since oscillator frequencies wx<y and toz
replace the w0 of the spherical problem. When this total electronic
energy is calculated as a function of jj, minima are found for both
prolate and oblate ellipsoids. The deeper of these two minima
determines the equilibrium value of ij, identifies which shape is
the more stable, and gives the equilibrium energy for the cluster.
The minima for the closed-shell clusters occur as expected for r)
Figure 3. Abundance spectrum for sodium: (a, top) continuous sweep
= 0. The equilibrium electronic energies for all open- and covering clusters 2-63; (b, bottom) clusters 44-105. In addition to the
closed-shell clusters may be plotted as a function of N. The second major shell closings at 8, 20, 40, 58, and 92, significant minor features
differences8 A2(N) then give the relative stabilities of the clusters appear at 26, 30, and 34.
and show peaks at the spherical shell closing and lesser features
at the spheroidal subshell closings.
and a number of transition metals,10,11 and semiconductors.25,26
Although a totally self-consistent calculation has not been made, In addition a number of reports have described mixed clus-
it appears that the configuration of the electron wave functions ters.16,2015,23,27,28 Much of the experimental work has dealt with
govern the predicted shapes. In the Clemenger-Nilsson model, the abundance spectra, which are related to the stabilities of
even the small clusters appear to have symmetries which correlate
clusters. Studies of properties have included electric29 and
closely with the results of detailed7 calculations. Thus, allowing
magnetic30,31 dipole moments, ionization potentials,32 and chemical
for the three-dimensional extent of the wave functions, clusters
reactivity.11,33,34 The cluster state has unique features of its own
3 and 4 are “prolate”, 5, 6, and 7 are “oblate”, 8 is spherical as
expected, and 13 is “prolate”. Martins et al. have described7 the
situation in terms of the p-like orbitals for the incomplete shell
for clusters N = 3-7. The shapes described above differ signif- (18) Begemann, W.; Meiwes-Broer, K. H.; Lutz, H. O. Presented at the
Xth International Symposium on Molecular Beams, Cannes, France, June
icantly from geometrical close-packing arguments. The important 1985. “Proceedings of the International Symposium on Metal Clusters,
geometry here is the shape of the collective electron distribution Heidelberg 1986”, Z. Phys. D 1986, 3, 109.
as in the case of the self-consistent spherical jellium model. Both
(19) Katakuse, I.; Ichihara, T.; Fujita, Y.; Matsuo, T.; Matsuda, H. Int.
models assume delocalized electrons confined within potential J. Mass Spectrom. Ion Processes 1986, 69, 153.
boundaries determined by a uniform structureless positive back- (20) (a) Brechignac, C.; Broyer, M.; Cahuzac, Ph.; Delacretax, G.; La-
bastie, P.; Woste, L. Chem. Phys. Lett. 1985, 120, 559. (b) Brechignac, C.;
ground. The progression of energy levels is similar except for the
Cahuzac, Ph.; Roux, J. Chem. Phys. Lett. 1986, 127, 445.
spheroidal splittings. Essentially the same physical picture ac-
(21) Muhlbach, J.; Pfau, P.; Recknagel, E.; Sattler, K. Z. Phys. B 1982,
counts for both major (spherical) and minor (spheroidal) features 47, 233.
in the abundance spectra. (22) Devienne, F. Marcel; Roustan, Jean-Claude, Organic Mass Spectrom.
1982, 17, 173.
Experimental Results (23) Martin, T. P. J. Chem. Phys. 1985, 83, 78.
At the present writing, a number of metal clusters and cluster (24) Meiwes-Broer, K. H., private communication.
ions have been studied; see the following reviews1’10-12 and con- (25) Bloomfield, L.; Freeman, R.; Brown, W. L. Phys. Rev. Lett. 1985, 54,
2446.
ference reports.13-15 Properties are known for alkali8,16 and (26) Heath, J. R.; Liu, Yuan; O’Brien, S. C.; Zhang, Qing-Ling.; Curl, R.
noble17,18 metals, some divalent19,203 and trivalent21-24 metals, lead,21 F.; Tittel, F. K.; Smalley, R. E. J. Chem. Phys. 1985, 83, 5520.
(27) Sattler, K. Surf. Sci. 1985, 156, 292.
(28) Kappes, M.; Radi, P.; Schar, M.; Schumacher, E. Chem. Phys. Lett.
(10) Phillips, J. C. Chem. Rev. 1986, 86, 619. 1985, 119, 11; J. Chem. Phys. 1986, 84, 1863.
(11) Whetten, R. L.; Cox, D. M.; Kaldor, A. Surf. Sci. 1985, 156, 8.
(29) Knight, W. D.; Clemenger, K.; de Heer, W. A.; Saunders, W. A.
(12) (a) Gole, J. T.; Stwalley, W. C., to be published in Advances in
Atomic and Molecular Physics, (b) Morse, M. D. Chem. Rev., in press. Phys. Rev. B 1985, 31, 2539.
(13) J. Phys. Colloq. 1977, 38, C2. (30) de Heer, W. A. Ph.D. Thesis, University of California, Berkeley,
1985.
(14) Surf. Sci. 1981, 106.
(15) Surf. Sci. 1985, 156. (31) Knight, W. D. Helv. Phys. Acta 1983, 56, 521.
(16) Knight, W. D.; de Heer, W. A.; Clemenger, K.; Saunders, W. A. (32) Saunders, W. A.; Clemenger, K.; de Heer, W. A.; Knight, W. D.
Solid State Commun. 1985, 53, 445. Phys. Rev. B 1985, 32, 1366.
(17) Katakuse, I.; Ichihara, I.; Fujita, Y.; Matsuo, T.; Sakurai, T.; Mat- (33) Geusic, M. F.; Morse, M. D.; Smalley, R. E. J. Chem. Phys. 1985,
suda, H. Int. J. Mass Spectrom. Ion Processes 1985, 67, 229. 82, 590.
Feature Article
Figure 4. Abundance spectrum for potassium: (a, top) clusters 3-51;
(b, bottom) clusters 50-100. Major shell closings are marked. Minor
features are seen at 26, 30, and 34.
as well as features which relate it to molecules on the one hand
and the bulk crystalline solids on the other. Questions such as
“at which size does a metal cluster begin to act like a metal?”
have stimulated several lines of work; for example, measurement
of electric dipole polarizability29 of alkali metal clusters indicates
that metallic screening is evident even in dimers. A study of
inner-shell autoionization in mercury clusters203 indicates that for
n < 8 metallic character has not yet developed.
The most prominent feature of the cluster state of metals is
the electronic shell structure, which has been observed in a variety
of pure and mixed metal clusters. The shell structure is reflected
in the abundance spectra,8 ionization potentials,32 electric dipole
polarizability,29 neutral cluster time of flight spectra,35 and
photofragmentation spectra.36
In the rest of this experimental section, we will concentrate on
a discussion of the abundance patterns (mass spectra) and the
ionization potentials which give promising prospects for a future
spectroscopy of clusters.
Abundance Patterns. Shell structure was first recognized in
the abundance patterns of sodium clusters. Features occurring
at N = 8, 18, 20, 40, 58, and 92 identify a series of particularly
stable clusters37 (Figure 3). The same features have also been
seen in potassium clusters 29 (Figure 4) and in potassium clusters
containing single atom sodium impurities16 (Figure 5). Corre-
spondingly a series of particularly stable positive cluster ions have
been seen in secondary ion mass spectra (SIMS) spectra for the
noble metals,17,18 for example, for silver at masses ,/V+ = 9, 19,
21, 35, 41, 59, 93, 139, and 199. The members of this second
series differ respectively from the first by one atom, and the
stabilities correspond to clusters born as ions, with stabilities
characterized by 8, 18, 20,... electrons. Negative ions show38,39
(34) Richtsmeier, S. C.; Parks, E. K.; Liu, K.; Pobo, L. G.; Riley, S. J. J.
Chem. Phys. 1985, 82, 3659.
(35) Clemenger, K., unpublished work.
(36) de Heer, W. A., unpublished work.
(37) Although 18 and 34 appear as shell closings in spherical models, they
are not prominent in the experimental spectra. Cluster 34 is calculated to be
distorted,9 and it appears in the abundance spectra as a definite but minor
feature. Cluster 18 is now thought to be spherical50 but is small in comparison
with 20, which is thought to be exaggerated by evaporation effects.
(38) Hortig, G.; Muller, M. Z. Phys. 1969, 221, 119.
(39) Joyes, P.; Sudraud, P. Surf. Sci. 1985, 156, 451.
The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 3145
Number of atoms per cluster, N
Figure 5. (a) Abundance spectrum for potassium clusters with sodium
impurities. The intermediate peaks represent mixed clusters containing
one sodium impurity. Shell closings are seen for clusters containing 8,
20, and 40 electrons. At higher mass resolution the minor features at
26, 30, and 34 are clear in the mixed clusters, (b) Pure sodium abun-
dance spectrum for comparison.
abundance patterns according to N~ = 7, 17, 19, etc. also cor-
responding to 8,18, 20,... electrons. It was explained previously1
how the observed abundance patterns in a properly formed neutral
cluster beam originate from relative cluster stabilities and local
thermodynamic equilibrium among neighboring cluster sizes. If
the equilibrium conditions are not met, distortions are observed
in the abundance patterns.
The existence of an energy gap following the filling of a
spherical shell implies an abrupt drop in the relative stabilities
and intensities of the clusters immediately following. Thus, steplike
or edge discontinuities are expected and observed. The well-known
abundance spectra for alkali metals now serve as a basis for
comparison with other spectra related to electronic shell structure;
for example, see ref 17. Enough is understood about the effects
of experimental conditions that the spectra can be used to diagnose
those conditions.
Source Conditions and Cluster Formation. The quality of
experimental results depends directly on the capacity and per-
formance of the apparatus. We describe, for example, an ap-
paratus1 which has proven to be exceptionally effective in pro-
ducing relatively undistorted high-intensity alkali cluster abun-
dance spectra. It employs a detector with high sensitivity and
low noise permitting the detection of low abundances and im-
portant fine features in the spectra. The clusters are produced
in a supersonic jet beam source. The cylindrical nozzle has a
uniform bore of 0.076 mm, which is equal to half the length.
Argon carrier gas pressures are between 1 and 10 atm. Typical
nozzle temperatures are ~ 100 K relative to the oven. The oven
source temperature is adjusted to give ~
5% mixing ratio of metal
vapor to carrier gas pressure. Final cluster temperatures are
typically 300-400 K.
~
Generally, in a seeded jet source, an inert gas is mixed with
a low concentration of, for example, alkali metal vapor and the
mixture is ejected.8,40'42~44a If the seed material can condense,
3146 The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 Cohen et al.

clusters will be formed in the expansion. This situation differs

from the pure vapor expansion,41 particularly because the carrier
gas can serve as a heat bath for the seed. Collisions between seed
particles facilitate the establishment of equilibrium among the
cluster species in the nozzle channel.1 The carrier gas mediates
the equilibrium and absorbs most of the heat of formation which
is converted into translational energy of the beam.36 Outside the
nozzle, the densities and temperatures drop rapidly. Since the
vapor density is much smaller than the carrier density, collisions
among the clusters will cease before the cluster carrier collisions
die out so that the cluster cooling continues after the cluster
formation processes stop. This final cooling freezes the distri-
bution.
Significant cooling of the vibrational states of the sodium trimer
in seeded molecular beams has been demonstrated443 for carrier
pressures ranging from 1 to 8 atm where it is observed that spectral
features which are broad at 1 atm carrier pressure become narrow
at 8 atm, and final temperatures are estimated to be around 20
K. Figure 6. Ionization potentials for potassium clusters 3-100. Note the
The relative heights of peaks in the abundance spectra are in drops in IP at major shell closings. Note also dear minor features at 26
and 30. Although the overall precision is 0.06 eV, comparative values
proportion to relative cluster stabilities reflecting the frozen
for neighboring clusters are good to 0.01 eV.
equilibrium distribution of clusters. Numerical estimates1 indicate
a formation temperature which is consistent with the actual
temperature in the nozzle channel. Although the seeded cluster jet source is a simple and reliable
if there is significant additional growth by agglomeration or method of producing a wide range of cluster sizes, its operation
by addition of atoms to the clusters which have already formed, requires high vapor pressures, and hence it is unsuitable for high
the abundance maxima will shift to larger numbers than predicted boiling point metals. Other cluster sources are described in ref
1.
by cluster stabilities. This may occur in a diverging conical
Photoionization. In the detector, clusters are photoionized and
nozzle,28'45,46 for example, tending to shift the features at 8 and
20 to 9 and 21. On the other hand, if the expansion cooling is focused on the entrance of the on-axis quadrupole mass analyzer
insufficient to stabilize the clusters which were formed in the nozzle (QMA) which is designed to pass 50% of the selected masses.
~

The range of the QMA is >4000 amu.

channel, evaporation of atoms or dimers may shift the maxima
to lower cluster numbers giving rise to maxima around 6,7 and
18,19 instead of 8 and 20. This is observed1,43 for excessively hot
nozzles or high mixing ratios. Since at a given temperature the
evaporation rates and stabilities are inversely related, at inter-
mediate temperatures evaporation will tend to enhance the high
stability peak at Ns at the expense of those clusters at Ns + 1 and
Ns + 2 immediately above in the sequence. This accentuates the
edges at 8, 20, and 40 in the Na and K abundance spectra.
The effect of different carrier gases on the production of sodium
clusters was studied43 for He, Ne, Ar, Kr, and N2. The heavier
noble gas carriers progressively increase production of larger
clusters. The nozzle temperature and mixing ratio were high
(35%) resulting in hot clusters. The effects of different gases on
the production was explained in terms of varying efficiencies in
removing the heat of condensation from the clusters.
Although the temperatures of clusters produced in seeded beams
have not been widely investigated,443 it is possible to estimate a
final upper temperature limit based on cluster stabilities. Since
the clusters in the apparatus being described1 survive the 2-m flight
from source to detector, the evaporation rate must be less than
103 atoms/s. An order of magnitude estimate of the evaporation
rate can be made by assuming that, per unit area, the clusters
evaporate at approximately the same rate as the bulk, which can
be estimated from the vapor pressure. Using the bulk vapor
pressure of sodium, it is found1 that for Na2o the vibrational
temperature must be less than 500 K.
(40) Knight, W. D.; Monot, R.; Dietz, E. R.; George, A. Phys. Rev. Lett.
1978, 40, 1324.
(41) Delacretaz, G.; Ganiere, J. D.; Monot, R.; Woste, L. Appl. Phys. B.
1982, 29, 55.
(42) Larsen, R. A.; Neoh, S. K.; Herschbach, D. R. Rev. Sci. Instrum.
1974, 45, 1511.
(43) Kappes, M. M.; Kunz, R. W.; Schumacher, E. Chem. Phys. Lett.
1982, 91, 413.
(44) (a) Delacretaz, G.; Woste, L. Surf. Sci. 1985, 156, 770. (b) Her-
mann, A.; Hofman, M.; Leutwyler, S.; Woste, L.; Schumacher, E. Chem.
Phys. Lett. 1982, 26, 2247. (c) Gole, J. L.; Green, G. J.; Preuss, D. R. J.
Chem. Phys. Lett. 1982, 26, 2247. (d) Morse, M. D.; Hopkins, J. D.; lan-
gridge-Smith, P. R. R.; Smalley, R. J. Chem. Phys. 1983, 79, 5316.
(45) Hagena, O. f.; Obert, W. J. Chem. Phys. 1972, 56, 1793.
(46) Brechignac, C.; Cahuzac, Ph., private communications.
(47) Daly, N. R. Rev. Sci. Instrum. 1960, 31, 264.
The light intensity is monitored continuously during data
collection and fed to the computer which provides a continuous
plot of corrected and normalized signal against photon wavelength
or energy as the light source is scanned by a computer-controlled
stepping motor. A shutter is provided to turn the arc lamp on
and off during laser irradiation in order to monitor the wave-
length-independent intensity of the detected cluster. A light
chopper occults the ionizing light at a 15-Hz rate for synchronous
lock-in processing in order to eliminate non-light-related signals.
The cluster beam intensities obtainable with the seeded source
and sensitive detector yield signals of >20000 counts/s for sodium
cluster N = 20 at detector noise levels of ~
1 Hz. The major
sources of noise are statistical fluctuations in the cluster beam
or light intensity. The detector lies approximately 2 m downstream
from the source, and the cluster beam flux at the detector is orders
of magnitude smaller than would be observed at the more com-
monly used shorter distances. This loss of intensity is more than
compensated for by the large source production and the sensitivity
of the detector. The original design, which was intended to provide
adequate path length for deflection experiments, has special ad-
vantages, for example, in assessing the expansion cooling at the
source and photofragmentation in the beam.
The light sources are a xenon arc lamp (with optional filter or
monochromator (2.5-5.0 eV at 12 nm resolution) or a tunable
CW laser. Although the xenon lamp output is low compared to
the HgXe lamp, it is superior to the latter because of the relatively
flat spectral output, which permits precise location of spectral
features without requiring elaborate deconvolutions. Ionization
potentials are determined by linear extrapolation.32'48
In recent years, considerable attention has been devoted to alkali
cluster ionization potentials (IP). The most recent results for K
clusters span a wide range from N = 3 to 101 (ref 32) (Figure
6) and exhibit several important features. Immediately following
each spherical cluster, the IP drops abruptly. The IP jumps at
the spherical shell closings N = 8, 18, 20, 40, 58, and 92 are
consistent with the abundance spectra. Although the absolute
error of the IP values may be comparable with the observed jumps,
it is evident from Figure 6 that the IP variation from cluster to
(48) Brechignac, C.; Cahuzac, Ph, Chem. Phys. Lett. 1985, 117, 365.
Feature Article The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 3147

cluster can be determined to an accuracy of ~0.01 eV.49 The TABLE I: Electron Eigenvalues (in eV) for 13- and 15-Atom
high accuracy permits the recognition of IP jumps at the larger Clusters0
cluster closings at 40, 58, and 92 and also fine structure features
in the IP curve. _Naij_ _Na1s_
Instrumental effects at the detector can produce distortions in state jellium cluster jellium cluster
the abundance spectra, although under common conditions the Is -5.037 (2) -4.805 (2) -5.097 (2) -4.933 (2)
-3.985 (6) -3.675 -4.104 (6) -3.930
spectra are independent of the ionizing light spectrum. Hence, Ip (6) (6)
cluster 9 (whose IP is below the IP for 8) appears to dominate Id -2.718 (10) -2.498 (6) -2.916 (10) -2.930 (4)
if -2.255 (4) -2.636 (6)
8 laser photon energy is set20b between the respective thresholds.
2s -2.265 (2) -2.195 (2) -2.505 (2) -2.433 (2)
Similarly two-photon ionization2015 produces a strong odd-even
alternation in the abundance spectrum which causes 9 to dominate “Degeneracies are noted in parentheses. The electrons occupy the
8 and 10, and raises 21 relative to 20. Although photodissociation lowest energy levels.
occurs at high laser fluence,20b’41 it is not an important factor in
spectra produced by broadband arc lamp sources.32,50
Implications for Spectroscopy. The spectra of dimers51,52,53
and trimers44a_d of alkali and other metal clusters have been
explored with considerable success. It was expected that the
spectra of larger clusters would be complex and congested with
vibrational and rotational effects and thermal broadening. Few
data are yet available for larger clusters except for measurements
of ionization potential. In addition to the recognition of IP jumps
at the spherical closings, new patterns emerge in variations of the
IP’s for the nonspherical clusters. For example, variations of the
IP are seen for the following sequences of four: 15-18, 23-26,
and 27-30, 41-44. Although the magnitude of these features is
smaller than the IP jumps at spherical clusters, they are seen
consistently and reflect fine structure of the energy-level system
of the clusters. They are also consistent with fourfold patterns
Number of Atoms, N
in the level structure derived from the Nilsson theory9 for
spheroidally distorted clusters. The case of N 12 which is
—
Figure 7. Calculated total energy per atom in the spherical jellium model
for sodium as a function of cluster size.
ambiguous in spheroidal theory is resolved in a three-dimensional
Clemenger-Nilsson analysis50 and is definitely predicted to be
stable relative to its neighbors as is observed. Hilckel molecular orbital (HMO) method; and LilV (N S 13)58
Furthermore, resolvable peaks50 are observed near the thresholds by the generalized valence bond formalism (GVB). The results
of certain clusters, that is, those following the spherical clusters for the equilibrium geometrical structures obtained from mini-
N = 40, 58, and 92. The intensities of these peaks at N = 59, mizing the total energies in the different calculations are usually
60, 61, and 62 are linearly proportional to 1:2:3:4 which indicates in agreement. For example, it is found in these studies that alkali
that every electron at the beginning of a new shell contributes metal clusters containing fewer than six atoms have planar
identically to the PIE curve. Similar behavior is observed at 93-96 equilibrium structures.
and indicated at 41-44. Single-particle levels begin to emerge There have also been some calculations of the electronic
even for the smallest clusters N = 3, 4, as pointed out in ref 32 properties for certain larger clusters with fixed high-symmetry
where one can also see evidence for partially resolved peaks at structures; and results are available for Na,59 Li,60 and Ni.61 It
well-defined energies which shift slightly as electrons are added is instructive to compare these fixed-structure results with jellium

successively to the shells. The shifts of these peaks with cluster
electron number gives further evidence for fine structure needing
refined theoretical models for interpretation.
Theoretical Results
As discussed previously, because of the complexities involved,
ab initio theoretical studies of the structural and electronic
properties of metal clusters have only been carried out for clusters
containing small numbers of atoms. In some cases, only a few
optimal atomic arrangements are considered. In particular, alkali
metal clusters have been examined by using various theoretical
approaches: Na v (N 2,..., 8, and 13)7,55 by the pseudopotential
=
results for the same size cluster. For example, if we focus on the
results for Na13 and Na15 clusters,59 the most striking feature is
the lack of directional bonding. Charge density plots59 illustrate
that the Na valence electrons are not localized around the atoms
but spread out over the cluster. Even though the structures for
Na13 and Na15 are taken to be bcc and fee, the electron charge
appears delocalized in the manner expected for a nearly free
electron-like system.
Another important comparison is the energy eigenvalues of the
Na13 and Nais fixed structures with the corresponding jellium
values. The results appear in Table I which lists the eigenvalues
and degeneracies. The results for the two comparisons are re-

method within the LDA; LiiV (N < 5)56 by the self-consistent-field,
molecular-orbital method (SCF-LCAO-MO) within perturbative
configuration interaction; (N < 14, M = Li —*• Cs)57 by the
(49) Commonly quoted experimental accuracies28 are not better than 0.1
eV which is inadequate to distinguish easily the largest of the IP jumps at 9,
18, and 20.
(50) Saunders, W. A. Ph.D. Thesis, University of California, Berkeley,
1986.
(51) Feldman, D. L.; Lengel, R. K.; Zare, R. N. Chem. Phys. Lett. 1977,
52, 413.
(52) Hermann, A.; Leutwyler, S.; Schumacher, E.; Woste, L. Chem. Phys.
Lett. 1977, 52, 418.
(53) Broyer, M.; Chevalyre, J.; Delacretax, G.; Fayet, P.; Woste, L. Chem.
Phys. Lett. 1985, 114, 447.
(54) Martins, J. L.; Buttet, J.; Car, R. Phys. Rev. Lett. 1984, 53, 655.
(55) Martins, J. L.; Car, R.; Buttet, J. J. Chem. Phys. 1983, 78, 5646.
(56) Rao, B. K.; Kharma, S. N.; Jena, P. Solid State Commun. 1985, 56,
731. Rao, B. K.; Jena, P. Phys. Rev. B 1985, 32, 2058.
(57) Wang, Y.; George, T. F.; Lindsay, D. M.; Beri, A. C., to be published;
Lindsay, D. M.; Wang, Y.; George, T. M„ to be published.
markably similar. For the bcc and fee structures, crystal field
effects split the tenfold spherical degeneracy of the Id states.
Otherwise, the same sequence of degeneracies appear in the jellium
and in the fixed-structure models. Even for the Id levels, the
splittings are small. Therefore, for self-consistent jellium calcu-
lations,62-65 we expect that the results will be similar both to a
(58) McAdon, M. H.; Goddard III, W. A. J. Non-Cryst. Solids 1985, 75,
149.
(59) Cleland, A. N.; Cohen, M. L. Solid State Commun. 1985, 55, 35.
(60) Redfern, F. R.; Chaney, R. C.; Rudolf, P. G. Phys. Rev. B 1985, 32,
5023.
(61) Melius, C. F.; Upton, T. H.; Goddard III, W. A. Solid State Com-
mun. 1978, 28, 501.
(62) Chou, M. Y.; Cleland, A.; Cohen, M. L. Solid State Commun. 1984,
52, 645.
(63) Beck, D. E. Solid State Commun. 1984, 49, 381.
(64) Ekardt, W. Phys. Rev. B 1984, 29, 1558.
(65) Chou, M. Y.; Cohen, M. L. Phys. Lett. 1986, I13A, 420.
3148 The Journal of Physical Chemistry, Vol. 91, No. 12, 1987
8 SO 34 40 58 68
Number of atoms per c luster,
cluster number N
Figure 8. Relative binding energy change A2(TV) vs.
for (a) lithium, (b) sodium, and (c) potassium.
rounded square well with depth approximately equal to the sum
of the bulk Fermi energy plus the work function and to a full
pseudopotential calculation if the pseudopotential is weak. Shell
structure on the whole survives the differences in these models
and dominates the total energy. The overall model and energy-
level scheme resemble those of a system with properties somewhere
between those of an atom and a solid.
It is the discreteness of the energy levels that gives rise to
discontinuous changes in the total energy as a function of the
number of atoms N. The splittings are determined by the electron
density of the jellium sphere or spheroid. Figure 7 displays the
total energy per atom for a Na jellium sphere as a function of
N. When the N value corresponds to a cluster with enough
electrons to completely fill a level (to close a shell), the total energy
per atom usually exhibits a minimum (Figure 7). The gaps in
the energy spectrum give the minima and stability at the special
values N = 8, 18, 20, 34, 40, 58, and 92.
Experimentally, if the clusters in the nozzle region are almost
in thermal equilibrium and the density distribution is unchanged
during the free expansion and ionization processes (i.e., ignoring
fragmentation and ionization cross section differences for different
clusters), the observed abundances should be closely related to
the second derivative of the total energy with respect to TV1
A 2{N)
In
f.v-lfv+l kT
where A2(TV) s 2E(N) E(N-1) £(TV+1), and E(N) and IN
- -
are respectively the total electronic energy and the observed
abundance intensity for the TV-atom cluster. The calculated1 A2(TV)
is shown in Figure 8 for Li, Na, and K where the peak positions
at TV = 8, 18, 20, 40, 58, 92 correlate excellently with the dis-
continuities in the mass spectra (Figures 3 and 4) for Na and K.
The peak at 34 in Figure 8 has only a weak apparent counterpart
in the experimental mass spectra.3 Experiment and theory ac-
cording to eq 10 are compared in Figure 9. The overall agreement
between theory and experiment for the mass spectra supports the
(66) Nilsson, S. G. K. Dan. Vidensk. Selsk. Mat. Fys. Medd. 1955, 29;
Gustafson, C.; Lamm, I. L.; Nilsson, B.; Nilsson, S. G. Ark. Fys. 1967, 36,
613.
Cohen et al.
0 10 20 30 40 50 60
Figure 9. Comparison of (a) experimental and (b) theoretical abundance
spectra for Na.
92
validity of the jellium approximation and the assertion that jellium
gives a satisfactory physical picture for alkali metal clusters.
N The effects of ellipsoidal distortions were mentioned earlier.
The application of Nilsson theory9 represents so far only a first
approximation, but symmetry arguments and correspondence with
experiment suggest that further extension of the jellium model
to include a self-consistent treatment of the distortions would be
a valuable theoretical advance.
The criteria for deciding the range of applicability of the jellium
model to clusters are fairly straightforward. Since the jellium
model is based on the assumption that the valence electrons are
delocalized and weakly interacting with the ionic potentials, it is
applicable to systems in which this assumption is satisfied. For
example, it is not expected to be a good approximation for clusters
containing only a few atoms. In these cases, the atomic ar-
rangements are important in determining the cluster properties.
Furthermore, the smearing of the ionic cores is a better approx-
imation for singly charged cores than for multiply charged cores
because the latter have larger Madelung sums which scale as the
square of the charge. With these points in mind, one does not
expect that the jellium model would be highly accurate for pre-
dicting the properties of small Al clusters. It is found67 that the
orbital structure of Alw (TV = 2-6) with equilibrium atomic
configurations displays some differences compared with results65
for an analogous jellium model. Differences of this kind are
expected and are not an indication that the jellium model is
inappropriate for larger clusters. The alkali metal clusters are
among the best candidates for applications of the jellium model.
The results of a recent calculation68 support some of the statements
made earlier. In this study, the variation of the structural part
of the total energy of alkali metal clusters is shown to be smaller
(10)
than the variation arising from the filling of discrete single-electron
energy levels, especially for TV > 10.
Hence, on the basis of a variety of theoretical calculations, it
is concluded that in free-electron-like clusters the origin of the
discontinuities in the mass spectra is not related to the geometric
packing pattern but to the electronic structure. The merit of the
jellium model is that it gives a sound description of the observed
shell structure and serves as a starting point for extensions and
improvements to explain more detailed properties. In nonideal
clusters, crystal field effects will split the highly degenerate levels
found for clusters with perfect spherical symmetry. If the pseu-
dopotential is weak, the splittings are small compared with the
-
(67) Upton, T. H. Phys. Rev. Lett. 1986, 56, 2168.
(68) Manninen, M. Solid State Commun. 1986, 59, 281.
Feature Article
gaps between different shells as in the case of Na13 and Na15.59
Instead of forming a shell composed of a single level for crystalline
examples, the shells are sometimes composed of groups of lev-
els,59,60 and these energy levels are filled in ascending order by
electrons. The experimental finding that clusters with even
numbers of electrons are, in general, more abundant than those
with odd numbers of electrons indicates that there is a tendency
to fill these energy levels with pairs of electrons of opposite spin,
and the spin-polarization energy is smaller than the level splittings.
In addition, the consideration of the crystal field effect is ex-
pected to decrease the discrepancies found between the observed
ionization potentials and values calculated from the spherical
jellium model. The calculated results62"64 are larger than the
experimental values by ~ 15% and tend to overestimate the drop
at shell closing numbers because of the neglect of effects such as
cluster deformations. In the study of metal surfaces using the
jellium approximation, it was found6 that including the effects
of the lattice pseudopotentials as perturbations reduces the cal-
culated work functions by ~10% in better agreement with ex-
periment. The same trend is expected for the cluster case. In
the spherical jellium model, the large drops in the ionization
potential occur only at major shell closing numbers. The inclusion
of crystal field effects may give rise to some subshell structure
and reduce the drop, but at this point, no estimate for the size
of the reduction is available. However, encouraging results have
been found when the discontinuous variations of the ionization
thresholds for K clusters are compared with the highest last
occupied energy levels calculated with the spheroidally deformed
one-particle potential discussed above. The shape of the variations
as a function of cluster size agrees very well. One point worth
emphasizing is that even when accurate pseudopotentials are used
self-consistently the standard calculations are still based on the
LDA, and in the case of calculations for atoms, this approximation
often overestimates the ionization potentials by ~0.1-0.3 eV.69
In addition, care must be exercised in studying excited-state
(69) Gunnarsson, O. J. Appl. Phys. 1978, 49, 1399.
The Journal of Physical Chemistry, Vol. 91, No. 12, 1987 3149
properties using the LDA since density functional theory is not
designed to deal with excitations.70
The self-consistent jellium model has also been used to evaluate
the static polarizability within the linear-response scheme.71"73
Theoretical values are typically too small by ~ 15-20%.' It has
been suggested74 that an approximate increase of 10% can be
~
obtained by including the lattice structure with pseudopotentials.
The size-dependence dynamic properties, e.g., photoabsorption
and photoemission cross sections, are also evaluated71,72 within
the jellium framework. Sum rules, collective multipole excitation,
and inelastic electron scattering for these metal clusters have also
been studied.75,76 Specific predictions are available; further
experimental work is necessary to test them.
Recent photoabsorption experiments77 are consistent with the
predicted split surface plasma resonance peak for spheroidal
clusters and verify in detail cluster-to-cluster variations in ab-
sorption cross section. Although the theoretical picture will be
improved by imposing self-consistency on the calculations, the
simple modified spheroidal harmonic oscillator model successfully
predicts a large number of experimentally observed facts.
Acknowledgment. This work (M.L.C.) was supported by
National Science Foundation Grant No. DMR8319024 and by
the Director, Office of Energy Research, Office of Basic Energy
Sciences, Materials Sciences Division of the U.S. Department of
Energy, under Contract No. DE-AC03-76SF00098, and (W.D.K.)
by the National Science Foundation Grant DMR8417823.
(70) Schliiter, M.; Sham, L. J. Phys. Today 1982, 36.
(71) Ekardt, W. Phys. Rev. Lett. 1984, 52, 1925; Phys. Rev. B 1985, 31,
6360.
(72) Puska, M. J.; Niemenen, R. M.; Manninen, M. Phys. Rev. B 1985,
31, 3486.
(73) Beck, D. E. Phys. Rev. B 1984, 30, 6935.
(74) Ekardt, W.; Penzar, Z. Solid State Commun. 1986, 57, 661.
(75) Bertsch, G.; Ekardt, W. Phys. Rev. B 1985, 32, 7659.
(76) Ekardt, W. Phys. Rev. B 1985, 32, 1961; 1986, 33, 8803.
(77) de Heer, W.; Selby, K.; Kresin, V.; Masui, J.; Knight, W. D. Bull.
Am. Phys. Soc. 1987, 32, 484.