Optical spectroscopy of copper clusters: Atom to bulk

M. Moskovits and J. E. Hulse

Citation: J. Chem. Phys. 67, 4271 (1977); doi: 10.1063/1.435365

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Optical spectroscopy of copper clusters: Atom to bulk
M. Moskovits and J. E. Hulse
Lash Miller Laboratories and Erindale College, University of Toronto, Toronto, Canada M5S lAl
(Received 14 June 1977)

Copper clusters containing two-five atoms and large colloidal particles of copper were formed within
matrices by co-condensing metal vapor with argon, methane, and dodecane onto a low-temperature
substrate. The electronic absorption spectra of the resulting solids were recorded and absorptions
belonging to individual aggregates of copper identified using a previously published calculation which
predicts the cluster distribution within matrices of given metal-to-host ratios. The "birth" of the band
structure of copper is clearly visible on going from the dimer upward, with Cu. already possessing many of
the features of the bulk metal.

Interest in the physical and chemical properties of
small atomic and molecular aggregates, especially metal
clusters, has increased almost catastrophically in the
past five years, partially as a result of theoretical and
experimental innovations which have allowed quantum
mechanical calculations to be performed for moderately
large clusters and the uv-visible and photoelectron
spectra of aggregates to be measured.
It has been recognized for some time that small clus-
ters play key roles in such areas as the homogeneous
nucleation and growth of macroscopic particles in the
gas phase, 1 where the early stages of nucleation are of-
ten undetected, the photographic process2 for which one
requires silver clusters of a minimum size before a
usable latent image is formed, and heterogeneous cata-
lytic reactions 3 which in many cases proceed on small
metal aggregates supported in a refractory oxide ma-
trix. Surface SCience, which nowadays is primarily
concerned with the physics and chemistry at single-
crystal surfaces, has also turned its attention towards
the properties of metal clusters as a result of the use
of small aggregates by theoreticians to model surfaces
in either surface density of states calculations4 or in
quantum mechanical calculations of chemisorptive bond-
ing. 5 In this manner interest was generated in such
questions as the transition from the "molecular" to the
bulk metallic state 6 and the onset of bulk properties.
The recognition that homogeneous and heterogeneous
catalysis have certain underlying similarities sparked
interest in the progress of the chemisorptive bond on
going from the case of ligands bound to single metal
atoms to that of a molecule bound to large metal clus-
ters. 7 This in turn resurrected such ancient queries
as whether or not the chemisorptive bond is local.
Molecular orbital calculations on clusters were pion-
eered by Blyholder 5 and Baetzold8 using the extended
Huckel technique. With the development of the scattered
wave Xex technique by Slater and Johnson 9 the number of
calculations multiplied rapidly, notably through the work
of Messmer, 10 Johnson, 10 and Rhodinl l ; and via Ander-
son's12 refinement of the extended Huckel technique which
combines two-body electrostatic atomic repulSions and
one-electron orbital energies. Simultaneously, uv-visi-
ble absorption spectra of metal dimers and unidentified
higher aggregates were reported by Pimentel (Li 2) , 13
DeVore (Mn2 , Fe2, Ni 2),14 Brewer (Pb2), 15 Andrews (Li 2,
Na2) , 16 Knight and Evener (Mg2), 17 Jansson (Pt2), 18 and
one of us (M. M. ) with Ozin (Cr 2, 19 Cu 2, 20 V 2 21 ). In addi-
tion, early gas phase work data are available for CU 2,22
Ag2,23 and AU2' 24 Luminescence from CU225 has also
been reported recently. An ESCA study by Mason and
Baetzold on Ag aggregates 26 has also appeared. The
preceding is only a partial list. The spectra of aggre-
gates greater than dimers but smaller than colloidal par-
ticles have been reported by US 27 for Nix and recently by
Schulze28 for Ag 3. In this paper we report the spectra of
copper clusters in the range Cu-Cu, and that of copper
colloid in solid argon and paraffin matrices.
EXPER 1M ENTAL
Details of the apparatus design have been given else-
where. 7 Briefly, copper vapor was generated by resis-
tively heating a tantalum filament on which fine copper
wire was wrapped. The copper was melted and outgassed
before the deposition substrate was cooled. Copper de-
position rates were monitored with a piezoelectriC mi-
crobalance. 29 Research grade Ar and methane (Mathe-
son) were used without further purification and spectro-
scopic purity dodecane was deposited from the vapor
above the vacuum degassed liquid. Vapor deposition
rates were regulated by means of a fine needle valve and
measured by noting the pressure drop in a bulb of known
volume. The deposition substrate was a LiF plate cooled
to a bottom temperature of lOoK by means of an Air
Products Displex closed-cycle refrigerator. Spectra
were recorded on a Varian Techtron uv-visible spectrom-
eter with 1. O-nm slits.
RESULTS
The deposition conditions under which matrices con-
taining small copper clusters could be formed lay in a
narrow range of gas-to-metal ratio and gas depOSition
rates. Outside these confines one obtained either well-
isolated copper atoms or such large aggregates that the
spectra were dominated by that of colloidal copper. In
argon, efficient small-cluster production was achieved
in the metal-to-argon ratio range 3-10 parts per 1000,
and for argon deposition rates between 0.04 and 0.1
mmole/h. With methane the range was somewhat
broader, extending between approximately 1 and 25
parts per 1000 Cu/CH, and gas deposition rate of approx-
imately 0.01 and 0.1 mmole/h. In dodecane only the
spectrum of colloidal copper was obtained, even at the
largest feasible paraffin-to-metal ratio.
The concentration range 1-10 parts per 1000 is a use-

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4272 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters

ful one in studying cluster formation since, as we have

shown elsewhere, 30 the absorbance of a species Cu,
when divided by that of Cu atoms will increase with total
metal concentration Mo approximately as MQ-1. The re-
sults in methane were found to be particularly amenable
to analysis in terms of this rule.
The uv-visible spectra of the products of cocondensa-
tion of Cu vapor with Ar in various concentrations are
shown in Fig. 1. An analogous set of results for Cu in
CH 4 is shown in Fig. 2. In both sets of figures the spec-
tra are dominated by an intense absorption triplet near
300 nm when the Cu/gas ratio is low. Weak features on
either side of this absorption grow rapidly as the metal
content of the matrix increases. The observed absorp-
tions are summarized in Table I. The low-energy lines
which we will later assign to CU z seemed under some
deposition conditions to be disproportionately large. _ _L -_ _ _ _ _ L--_----L-____ ~~ ____- L I
This, we feel, is due to the fact that under some circum- 200 300 400 500 600 nm
stances a large fraction of the copper vaporizes as the FIG. 2. Portions of the uv-visible absorption spectra of
dimer. This results in spectra such as the one at the methane matrices containing copper. Metal to gas ratios in-
bottom of Fig. 1 in which CU z dominates the spectrum, crease top to bottom. Ordinate is absorbance in arbitrary
dwarfing even Cu lines. The conditions under which this units. Some lines belonging to Cu are suppressed for clarity.
happened could not be easily reproduced. In general,
inordinate quantities of CUz, were formed when the metal
was vaporized at low temperatures. A mass-spectro-
scopic study is underway to help clarify this phenomenon.
The spectrum obtained after cocondensing copper va-
por with dodecane is shown in Fig. 3. This spectrum is
different from those shown in Figs. 1 and 2. No trace
remains of the bands near 300 nm nor of the plurality
of absorptions on either side of that wavelength. The
spectrum slopes gently upward towards high energies
with two broad features at approximately 210 and 600
nm.
The spectral changes resulting from warming a Cui
CH 4 matrix to various temperatures are shown in Fig.
4. Warming Cu/Ar matrices caused a decrease in the
lines belonging to Cu (see later) and eventually produced
colloidal copper with little growth in the other spectral
bands. For temperatures near the boiloff point of the
I matrix, however, all bands in the spectrum dropped
sharply in absorbance to be replaced by those of col-
I 1
loidal copper and two new features, as shown in Fig. 5.
I \

~u
DISCUSSION
Copper atoms
The uv-visible spectrum of Cu atoms isolated in solid
argon has been reported by several workers. 31-33 That

!\

-'---
300 400 500 600 nm
---L -------- .~~------
200 300 400 500 FIG. 3. Portions of the spectrum of Cu in dodecane (upper
nClinometers curve). The spectrum of copper colloidal particles in dodecane
FIG. 1. Portions of the uv-visible absorption spectra of argon calculated using the method outlined in Ref. 27 and Johnson and
matrices containing copper. Metal to gas ratios increase top Christy's44 values for the optical constants of bulk copper
to bottom. Ordinate is absorbance in arbitrary units. (lower curve).

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 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters 4273

TABLE I. Wavelengths and assignments of the absorptions observed in argon and methane matrices con-
taining copper.

Cu
Relative
A nm Gas phase A (argon) A (CH() intensity Assignment
Assignment (gas) (gas)~ intensity (nm) (nm) (CH 4) (refers to Ar)
2PI/2 (3d I 04pl) 327.4 0.31 306.2 320.0 1.0 X2~ 112 -A 2713/2 of ArCu*
2P3/2 (3d 104pl) 324. 8 0.64 301. 8 314.3 0.9 2
-B 71 1/ 2
298.0 310.1 0.7 -C2~1'2
305.5 0.3
301.3 0.05
4p 3/2 (3,jl4s 14p l) 249.2 0.029 238.3 242 O. 02
233.6
4Pl/2 (3Jl4s14pl) 244.2 0.0057 229.3
4D1/2 (3Jl4s14pl) 222.6 0.0078 220.7
2PI/2 (3Jl4s14pl) 218.2 0.0160 218.0
2P3/2 (3,jl4s 14p l) 217.8 0.022 211.8 216 0.2
207.3 211 } 0.5
210

Cuz CU3 CU4

Anm Anm A nm Anm A nm A nm
(Ar) (CH 4) Assignment Calculated" (Ar) (CH 4) Assignmentb (Ar) (CH 4) Assignmentb
400 380} {d7f 6 -SU. 460 500
376
533l
404)
I-II
402 424
272
I-II
I-III
SU -SU
6 U 490
355 du6 -suU 350 335
283 SU6 -P71 u 280 262
236 256 dUU -pu6 240 234 280l
260
I-III
221 dUU -P7r6 200 230
221 227

"Reference 31. bSee text. "Reference 43.

of Cu in CH 4 has not, to our knowledge, been reported.
For Cu in Ar, the spectra consist of a prominent triplet
centered around 300 nm, a slightly smaller doublet at
about 210 nm and several rather small peaks in between.
Our own spectra of Cu in Ar are similar to those previ-
ously reported except for improved resolution of the
small features. Occasionally, weak lines are seen on
the low-energy slope of the 300 nm triplet. 31 These, we
find, disappear upon annealing and probably arise from
copper isolated in nonequilibrium phases of solid argon.
(A similar "red" triplet is reported for isolated alkali
atoms. See, for instance, Ref. 13.)

~ __ L~ ____
·~~,o nm
200 300 400 500 600 nm
FIG. 5. Portion of the spectrum of a Cu in Ar matrix after
FIG. 4. Spectra showing the effect of warmup on the cluster prolonged warmup at a temperature close to the matrix boil-
distribution within a Cu in methane matrix. Warmup time in- off point. The spectrum before warmup was similar to that at
creases top to bottom. the top of Fig. 1.

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4274 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters
The spectrum of Cu in CH 4 is similar to that of Cu in
Ar except that the triplet at around 300 nm is replaced
with a quintet whose structure persists even on anneal-
ing. We shall discuss Cu in Ar first.
The spectra of isolated atoms are usually discussed
by correlating the absorption lines of the matrix with
those of the gas phase atom. This procedure has been
formalized by Gruen 31 and named AMCOR. Broadly, the
spectrum of isolated atoms is expected to be similar to
that of the gaseous atom, as regards both line intensity
and position, provided that one corrects for the "matrix
shift" arising from nonspecific interactions between
host and guest and for the degeneracy of the excited state
(if the intensity is obtained from emission). Although
this procedure yields a good overall understanding of the
spectra of isolated atoms, it fails quantitatively and even
qualitatively in some important ways. So, for instance,
the line at 207 nm of Cu in argon, usually assigned to the
2S1 /2 - 2P3 /2 (3cf4s14pl) transition, is roughly 60% as in-
tense as those at 298, 302, and 306 nm which are as-
signed to the2S1/2-2Pl/2,3/2 (3d 10 4p 1) transition. In the
gas phase, on the other hand, the line associated with
the former transition is less than one-tenth as intense
as that of the latter. The fact that the 2S1/2-2P 1/ 2,3/2
transition forms a triplet rather than a doublet, as in
the gas phase, is another feature of matrix-isolated
atoms whose origin is not yet fully agreed upon and
which is not conveniently obtained from AMCOR. The
problem of 25 - 2P triplets is not a new one. Similar
triplets are obtained for alkali atoms in rare gase ma-
trices. 13.34 (With the alkalis one often obtains more than
one triplet or sometimes even quintets. These, how-
ever, reduce to a single, well-defined triplet on anneal-
ing. )
For a 25_ 2p transition to be a triplet one must either
trap Cu atoms in more than one matrix site or remove,
somehow, the degeneracy of the p orbitals of the Cu.
The cubic environment around all the usual sites in a
regular, face-centered cubic crystal such as that of
solid argon or solid methane does not lift the degeneracy
of p orbitals. Several proposals have been made to ex-
plain the observed triplet structure of 25_ 2p absorptions.
Although, in the main, these have been directed towards
isolated alkali atoms, similar arguments apply to group
IB atoms as well. Among these are (i) multiple trapping
sites; (ii) a static distortion of the matrix ariSing from,
for instance, a local change in crystal structure from
ccp to hcp,33 or as a result of a vacant argon site next
to the metal atom 35 ; (iii) Jahn-Teller effect arising from
the interaction of the excited metal atom with normal vi-
brations of the host of the required symmetry36; and
(iv) non-nearest-neighbor, guest-guest interactions. 13
The last was disproved by Brewer and Kin~2 by codepos-
iting more than one group IB metal together and noting
that the 2S - 2 P triplet remained unchanged. Moreover,
the ESR studies of Kasai 37 indicate that Cu in solid argon
occupies a single, highly symmetric site, precluding
static, ground-state perturbations of the atom and also
multiple sites. Kasai's work constrasts with ESR studies
on trapped alkali atoms which indicate the presence of
several sites as borne out by the uv-visible spectra
which show several 2S _ 2P triplets. 38
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The Jahn-Teller explanation was revived by Belyaeva
et at. 39 to explain the fluorescence spectra of isolated
Li atoms. These show Stokes shifts of approximately
4000 cm- 1 and no triplet structure. The separation be-
tween components in the 2S - 2P triplet of all group IA
and IB metals in Ar exceeds 200 cm- 1, We do not be-
lieve that vibronic coupling with the host can give rise to
such a large split nor is a spin-orbit split of the ob-
served magnitude feasible in Li interacting nonspecifical-
ly with its host. We therefore reject the Jahn-Teller
explanation and propose the observed triplet to be caused
by exciplex formation between the excited Cu (or alkali)
atom and one of its rare-gas neighbors. The excited
compound so formed may nevertheless be fluxional, with
the Cu bonded to only one rare- gas atom at anyone time.
A Cu*Ar bond of mainly Cu-4p and Ar-3d character (4d
for Kr and 5d for Xe) gives rise to three molecular
states: 22:: 1/ 2, 2nl/2' and 2n 3/ 2. Such exciplexes are well
known in alkali metal/rare gas systems. 40 Moreover,
the potential energy calculations of Baylis 41 and experi-
mental work due mainly to Gallagher 40 indicate that the
22::1/2 state of alkali-rare-gas complexes is dissociative
while the two (spin-orbit) 2rr states are bound. Vibra-
tional fine structure has even been detected in both the
absorption spectrum to and emission spectrum from the
21T3/2 state of CsAr. 40
Our proposa~, therefore, is that the Cu 2S_2P transi-
tion in argon is in fact three transitions cooresponding
to (Cu) 25 (formallyX 22::1/2)-(Cu*Ar)22:: 1/ 2, 2n3/2' 2nl/2'
and the components of the resulting triplet are split even
farther by the noncubic environment left behind as a re-
sult of the unique interaction between the Cu and one of
its argon neighbors. Assuming this model to hold for
both Group IA and IB metals, we can now understand
both the large Stokes shift and the single band structure
observed in the fluorescence spectrum of isolated Li. 39
Presumably, nonradiati ve processes depopulate all but
the lowest vibrational level of only one of these states
(perhaps the 2n3/2 state), which radiates to the dissocia-
tive ground state.
In the gas phase the 22::1/2 state of the alkali-noble-gas
complexes is highest in energy. Matrix shifts are suffi-
ciently large, however, to place that state below or be-
tween the other two in energy. We feel, however, that
spin-orbit coupling is not large enough in Cu*Ar to war-
rant assigning the outer two components of the triplet to
the 2n1 / 2,3/2 states.
A complete assignment, then, amounts to deciding
whether the highest or lowest energy transition involves
the 22::1/2 excited state. Our data cannot resolve this
dilemma. Interpreting recently published data of Kolb
et al. 33 in terms of our model, however, can simulta-
neously provide us with an assignment and help ration-
alize their data, Kolb found that the peak positions of
the two low-energy components of- the triplet belonging
to Cu in Kr and Xe decrease in energy with increasing
matrix temperature while the highest energy component
increases with increasing temperature. For Cu in Ar
the highest energy state decreases slightly while the
lower two decrease rapidly with increasing temperature.
By assuming that the interaction between the excited
 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters
" in Fig. 1) to Cu2. That assignment is incorrect, how-
R CUs ) grow in on warmup.
FIG. 6. Schematic representation of the potential for the
ground state and three excited states of CuAr vs internuclear
separation. The solid curves are similar to what one would
expect in the gas phase, the dotted curve represents the re-
pulsive interactions with the surrounding host suffered by the
two constituent atoms of the CuAr molecule at large separation.
copper atoms and their remaining noble gas neighbors
(with which they interact nonspecifically) is attractive,
and making reference to Fig. 6, one sees that as the
temperature is raised, increasing the host-host distance,
the nonspecific interaction between Cu* and its neighbors
decreases. This, in turn, increases the strength of the
Cu*-noble gas-atom bond in the exciplex and decreases
its bond length. If the highest energy component of the
triplet is assigned to the excited 2.0 1/2 repulsive state,
then, depending on the initial internuclear distance, one
can have the peak positions of the lower two components
decrease in frequency while the upper increases.
Extrapolating these arguments to the Cu/CH 4 system,
a similar exciplex may be formed whose bond has mainly
Cu 4p and CH 4 IT2 character. The latter state is even
closer in energy to the Cu 4p state than the 3d state of
Ar, implying even larger separation between the compo-
nents of the multiplet of Cu *CH 4 than for Cu* Ar, as is
observed. In contrast with the latter, the complex with
methane may have several forms according to the align-
ment of the hydrogen atoms with respect to the Cu-C
axis, resulting in more than one triplet. If, for instance,
only two are preferred; a C 3V and a C 2v complex, say,
then, in principle, a sextet would result made up of two
triplets: 2Al ZEI/Z' 2ES/2 for the former and a zA h ZBr,
2 B z for the latter. (Actually, owing to spin-orbit cou-
pling, each of these components is a Kramers doublet
whose degeneracy can only be removed magnetically.
The zA l of the C3v complex is formally a 2E 1 /2' So too
are the three states of the C2v complex.) The 2Al states
in the two forms would presumably be dissociative as in
the C.. v case and may therefore coincide in energy,
yielding the observed quintet. By similar arguments
to those above, the high-frequency lines observed in the
spectra of Cu in Ar and CH 4 also belong to the respective
exciplexes. The intensities of the transitions would de-
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4275
pend, of course, on the magnitude of the Franck-Condon
factors pertaining to the transition and good correlation
between the intensities of the electronic bands of the
matrix-isolated atoms and those in the gas phase would
not necessarily be expected.
The frequencies and assignments of bands associated
with Cu isolated in Ar and CH 4 are given in Table I.
CU2. CU3, and CU 4
Lines in the spectrum of matrix-isolated Cu other
than those belonging to single Cu species have been re-
ported by several workers 42 • 2o and attributed to Cu
clusters. One of us (M. M.), for instance,20 assigned
all but two of the "extra" lines (similar to those shown
ever; several of the bands in the spectra belong to Cu 3 •
Moreover, bands belonging to CU 4 (and perhaps even
The rationale that we use to determine the size of a
cluster giving rise to a particular band was outlined by
us in Ref. 30. Broadly, the absorbance of a line be-
longing to CUn when divided by that of a line belonging
to Cur, will depend on Mo, the metal-to-gas ratio ap-
proximately as
AcuJAcu ex M~ ,
where Cl is a number between x - 2 and x-I in value,
and closer to the latter, Mo is the metal-to-gas ratio,
and A denotes absorbance. So, a plot of 10gA cu/A Cu
versus 10gMo will be a straight line of slope approxi-
mately 0, 1, and 2 for, respectively, an absorption of
Cu, Cua, and Cu 3 • The above expression refers to spec-
tra obtained before warmup and was obtained by assum-
ing the clusters to form from monatomic copper in the
yet unfrozen layers of the matrix or the cooled gas phase
immediately above it. (One would have to modify the
analysis somewhat should sizeable quantities of CU 2 ex-
ist in the gase phase. )
The spectra of Cu clusters in CH 4 show fewer over-
laps than those in Ar. We will therefore proceed by dis-
cussing that system. Analyzing the Cu in CH 4 spectra
in the manner outlined above, we see, for instance (Fig.
7), that the line at 221 nm belongs to Cu, those at 256
and 380 nm to Cu2 , and those at 227, 260, and 533 nm
to Cu3 • Because some bands overlap, clear-cut assign-
ments of the features near 280 and 400 nm could not be
made using the above method alone and warmup data had
to be used to help separate bands belonging to aggregates
of different sizes. Presumably all lines belonging to a
single species would grow or decay together on warmup.
A typical warmup result is shown in Fig. 8. From it and
results of similar experiments were deduced that a line
at 260 nm (which forms part of a doublet) belongs to CU 3
as does a line centered near 280 and 404 nm. In addi-
tion, the weak lines centered at approximately 335 nm
probably also belong to CUs • On prolonged warmup two
lines at approximately 272 and 424 nm grow in, attaining
considerable size (Fig. 4). These we attribute to Cu 4 •
For clarity of presentation and subsequent discussion,
we show the spectra of the various clusters separately
in Fig. 9. Other lines have undoubtedly been missed in
4276 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters
-1 o As mentioned previously, no substantial growth of the
log Mo
FIG. 7. A plot of -logA/A 216 vs 10gMo. Ax, A 216 , and Mo
are the absorbance due to a cluster band, that of the Cu line
absorbing at 216 nm and the total metal to gas ratio. The last
in arbitrary units. Open circles, filled circles, and triangles
indicate, respectively, the absorbances of the 221 nm band of
Cu, the 283 nm band of CU2' and the 533 nIT! band of Cu 3.
the forest of bands occupying our spectral region.
The spectrum of Cu in Ar is similar to that of Cu in
CH 4 • The matrix shifts are, of course, different in the
two media, causing the band positions and, at times,
the severity of overlap to differ. The correlation of
bands for the two environments is given in Table I.
There are no discrepancies except that in Ar it is clear
that the band attributed to CU2 which comes at 380 nm in
methane is at least two bands which, in Ar, are centered
at approximately 345 and 400 nm, respectively. The lat-
ter is quite likely the X -A progression reported by
Kleman and Lindkvist 22a for gaseous CU 2 with ~o coming
at 490 nm. This band has been assigned by Aslund et
al. 22b to the I~; - Inu (d1T,- SGu ) transition. We concur
with this assignment. The only other likely one, that of
SG,- SGu , would not show such large vibrational fine
structure since in the excited state the Cu-Cu single
bond, which has mainly Cu 4s character, is essentially
absent. On the other hand, the d1T,- SGu transition, and
for that matter any transition from the d manifold, is
expected to weaken the Cu-Cu bond only slightly. De-
spite many attempts, we have not been able to find vi-
brational fine structure in either of our two bands (or
indeed any of the Cll,; absorptions). If, however, we
take the low-energy edge of the 400-nm band as our val-
FIG. 8. The change in ab-
sorbance of the 227 nm (filled
circles), 553 nm (open cir-
cles) , and 256 nm (triangles)
bands vs warmup time. The
first two bands belong to CU3;
the last to CU2'
warmup time
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"
f\
~
~\ (U4
211 424
A
W Lfl')
-~-
m
~-----............-
404
/~ CU 3
5'3
2'><, ,283 3BO
AJl ~-'-
200-'---300--406- ---sao' "---'--6-66
CU2
nm
FIG. 9. A schematic representation of bands assigned to Cu 2,
CU3 and Cu 4 •
ue of ~o, we arrive at a matrix shift (Vrnatrlx - Vga.) of
1960 cm- I •
Cu cluster species in the range CU 2-CU 4 was observed
on warming the Cu in Ar matrices. On prolonged warm-
up one obtained instead a broad band centered at about
233 nm and a weaker band at 281 nm. These may belong
to CU 5 or higher species. The breadth and position of
the former foreshadow the spectrum of colloidal copper.
SPECTRAL ASSIGNMENTS
Since molecular states are labeled with irreducible
representations of the group to which the molecule be-
longs, one must know the geometry of the clusters be-
fore formal spectral assignments are possible. Our data
do not yield geometries. Molecular orbital calculations
by Baetzold for Agx 8 and Anderson for CUr 43 indicate,
however, that close-packed geometries seem to be less
stable than linear or zigzag forms of the clusters. The
latter, for instance, finds that CU 3 and CU 4 have C2v and
C 2h structures, respectively, with very small deviations
from linearity. Because of the serious approximations
made in those calculations, one cannot take these shapes
to be conclusive. It is, however, extremely useful to
use energy-level diagrams, such as those calculated by
Anderson on the basis of these geometries, in discuss-
ing the spectra. Other quantum-chemical calculations
have been performed on clusters of copper as well6 and
will be referred to as required.
Fig. 10 shows the energy levels of Cu, Cu2 , Cu 3 , and
CU 4 as calculated by Anderson. 43 The eigenenergies of
the clusters seem to fall into three groups of levels.
The lowest energy group (1) consists of filled states hav-
ing mainly sand d character. The middle set of states
(II) is empty and possesses largely S character with some
p as well. The highest set (III) consists of unfilled states
of p character with some S character. These rather
arbitrary divisions are shown in Fig. 10. The gap be-
tween the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO) de-
creases as one proceeds from CU 2 to Cu 4 • (In the last,
in fact, this transition is predicted to lie in the near ir. )
This gap should, 'in fact, reduce to a very small quantity
as bulk copper is approached (as shown by Baetzold for
Ag), with regions I and II forming the filled and empty
halves of the conduction band of copper. Likewise, re-
gion III forms the empty sp band of the bulk metal.
The HOMO-LUMO transition should therefore recede
quickly into the infrared, broadening as it goes, until
 M. Moskovits and J. E. Hulse: Spectroscopy of copper clusters 4277

o Cu CU2 CU4
CU3

-5
~lT'-

pu-
~n-
p~ - ) ;)1
"·-1 '" 15(, •-I'+ " :lJ7
1100
535 .180
111. }
-s 380
s
"'1.1:
-
~cr

-10
-d
.11" ...
.(;
.r=
"to
45- ! \
eV ,IlT
40"

FIG. 10. The eigenvalue spectra calculated by Anderson43 for CU2' Cu3, and Cu4. The VOIP's of the Cu 3d, 4s, and 4p used in
the calculations are also shown. The highest filled orbital is indicated by either a single or double vertical arrow for hall and
fully filled orbitals. The spd labels next to the levels of CU2 indicates their major character. In fact most levels marked d and p
contain substantial s character and the su and su* states contain a great deal of d and p character, respectively. Large vertical
arrows indentify possible transitions giving rise to the observed bands indicated beside each.

in the bulk it is replaced by the spectrum of the free
electrons that extend from the far ir to the visible. This
picture agrees very well with our experimental results
if we identify one of the broad bands of CU 2 in the vicinity
of 400 cm-1 (all wavelengths will refer to the Cu in
methane system) with the sa, - sau transition (i. e., a
region I - II transition). In the context of bulk copper,
this absorption is an intraband transition. (The other
band of CU 2 in that region is probably the sa- pa* transi-
tion.) The CU3 band at 533 nm is the HOMO- LUMO
transition in that molecule which begins the trek to low
energies on its way to forming the Drude region of the
spectrum of bulk copper. CU 4 has two states in region
II. The HOMO- LUMO transition is already in the near
ir and the band at 424 nm arises from a transition to
what may be termed an incipient conduction band upper
boundary.
The other observed transitions are assigned in a gen-
eral way in Fig. 10 and Table I. Because there are
many closely spaced levels in the energy diagrams, firm
assignments are unjustified. Briefly, with the exception
of the 355 nm transition in CU 3 which is still a region I-
n transition, all others are region I-III transitions, i. e.
incipient interband transitions. These transitions re-
main essentially in the same region of the spectrum
(200-300 nm) in all copper clusters from CU2 to the
bulk.
A spectrum of bulk copper in colloidal form is shown
in Fig. 3. The broad feature extending from 200 nm to
lower energies is due to interband transitions. The fea-
ture at approximately 600 nm is the so-called optical
conduction resonance and is due to conduction electrons
(Le., intraband processes). Its position and prominence
(in fact the entire spectrum) can be calculated with con-
siderable accuracy as described in Ref. 27 using the op-
tical constants of bulk copper given by Johnson and
Christy.44 Such a calculated spectrum is shown in
Fig. 3.
Although small copper aggregates already possess
many of the features displayed by bulk copper, many
aspects of these clusters such as the energies and spd
compositions of its valence orbitals vary dramatically
with cluster size. This behavior has been put to good
use in heterogeneous catalysis where it is known that
catalysts containing particles of different mean radius
often behave quite differently. 45 One would expect,
moreover, that the change in electronic properties per
atom would be most dramatic in very small clusters
such as those we described. Mass filtering these ag-
gregates and isolating them in an appropriate support
so that all the clusters within a sample are of uniform
size could yield a spectrum of catalysts each containing
the same kind of metal but exhibiting totally different
catalytic properties. Such a prospect is close at hand.
ACKNOWLEDGMENTS
The authors are indebted to the National Research
Council of Canada, the Research Corporation, and the
Atkinson Foundation for financial support. One of us
(J. E. H. ) wishes to thank the N. R. C. C. for a scholar-
ship. The technical assistance of K. Molnar, T. Hig-
son, A. Campbell, and M. Mittelstaedt is also greatly
appreciated. Thanks are also due to professor A. B.
Anderson for allowing us to quote the results of his cal-
culations on copper clusters prior to their publication.
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