Relativistic Effects on Geometry and

Electronic Structure of Small Pd n

Species ( n = 1, 2, 4)

CHUANYUN XIAO, SVEN KRUGER,

THOMAS BELLING,

MARKUS MAYER, NOTKER ROSCH

Lehrstuhl fur
D-85747 Garching, Germany
Theoretische Chemie, Technische Universitat
Munchen,

Received 19 February 1999; accepted 22 April 1999

ABSTRACT: Relativistic effects on the properties of small neutral Pd n species n s

1, 2, 4. and Pd 2y have been examined for the first time at the all-electron level by
performing scalar-relativistic and nonrelativistic density functional calculations using a
gradient-corrected density functional. Relativistic effects are found to be important: They
lead to a contraction of bond lengths, increase of vibrational frequencies, and a significant
enhancement of binding energies. While relativistic effects are quite uniform for several
states of Pd 4 , they vary for the states examined for Pd 2 , leading to a change of ground
state due to relativity. The calculated relativistic properties of Pd 2 and Pd 2y are in good
agreement with available experimental data from mass spectrometry and photoelectron
spectroscopy. For Pd 4 three-dimensional structures are found to be preferred to planar
ones and many nearly isoenergetic isomers exist. 1999 John Wiley & Sons, Inc. Int J Quant
Chem 74: 405416, 1999

Key words: cluster; relativistic effects; density functional calculation

Introduction

ransition metals TM. in the form of highly

disperse small particles form the active component of many heterogeneous catalysts w 13x .

Correspondence to: N. Rosch.

Contract grant sponsors: Deutsche Forschungsgemeinschaft;

Fonds der Chemischen Industrie.
International Journal of Quantum Chemistry, Vol. 74, 405416 (1999)
1999 John Wiley & Sons, Inc.

Other application areas where small TM particles

have recently found great interest are nanostructured materials, molecular electronics, and sensors
w 4x . Stimulated by these practical interests as well
as by the particular properties of clusters containing only few atoms, the electronic and geometric
structure and reactivity of TM clusters have been
the target of many theoretical and experimental
studies in recent years w 57x . Often TM clusters are
modified due to interactions with a supporting or

CCC 0020-7608 / 99 / 040405-12

XIAO ET AL.
stabilizing surrounding, like a solid surface, a zeolite framework, or a ligand shell. For a thorough
understanding of these species, detailed knowledge of the properties of pure TM clusters is a
necessary prerequisite as reference and theoretical
studies form one source of such information. Computational investigations of TM clusters, however,
are very challenging due to the normally large
number of low-lying electronic states that arise
from the open d shells of the TM atoms. Consequently, an accurate treatment of electron correlation is mandatory. In addition, relativistic effects
may be important for the second-row TM elements, and they have to be considered for thirdrow TM elements w 8x .
In this work, we report results of relativistic and
nonrelativistic density functional DF. calculations
of Pd n n s 1, 2, 4. as well as of Pd 2y employing a
gradient-corrected exchangecorrelation functional. This is the first such investigation consistently carried out at the all-electron level. Our
study is mainly devoted to examining relativistic
effects on the geometric and electronic structure of
these TM species. The importance of relativity for
a correct description of Pd compounds has been
pointed out in some previous studies w 911x where
relativistic effects were incorporated by means of
relativistic effective core potentials RECP.. On the
other hand, in a recent nonrelativistic examination
of Pd n n s 13. relativistic effects were claimed
to be negligible w 12x . To verify our results, comparison with experimental data will be made. The
results of other theoretical studies will be briefly
reviewed in comparison to our calculations, aiming at a clarification of open questions like the
ground-state geometry of Pd 4 . In the following
section we describe our methodology and computational parameters. The third section presents the
discussion of our results as well as a critical
overview of comparable computational work. We
summarize our conclusions in the last section.

Computational Details
All-electron calculations have been carried out
using the program ParaGauss, a newly developed
parallel implementation of the linear combination
of Gaussian-type orbitals DF LCGTO-DF. method
w 1315x . For the exchangecorrelation functional,
we used the VoskoWilkNusair VWN. w 16x pa-

406

rameterization of the local density approximation

LDA. together with density gradient corrections
to the exchange w 17x and the correlation w 18x functionals Becke-Perdew BP.; this gradient-corrected
functional was applied self-consistently in all calculations. The LCGTO-DF method employs two
different Gaussian-type basis sets: one to represent
the KohnSham KS. orbitals and one to fit the
charge density when calculating the classical
Coulomb interaction of the electrons. The nonrelativistic and relativistic orbital basis sets used for
Pd were obtained by contracting a 18 s, 13 p, 9 d .
basis to w 7s, 6 p, 4 d x based on nonrelativistic and
relativistic atomic orbitals, respectively, using a
generalized contraction scheme w 19x . The effect of
f-type polarization functions in the orbital basis set
exponents 1.5, 0.6, and 0.24. was tested by a
relativistic calculation of Pd 2 . This extension of the
orbital basis set led to a contraction of the bond
and to an increase of the binding
length by 0.020 A
energy by 0.080 eV. The auxiliary fitting basis set
was derived from the orbital exponents in a standard fashion w 13x and augmented by a standard set
of p- and d-type polarization functions w 19x .
Spin-polarized calculations were performed
throughout to account for the open-shell structure
of some of the Pd n species. Relativistic calculations
were carried out using the self-consistent relativistic variant of the LCGTO-DF method w 20, 21x . The
relativistic version is based on a reduction of the
full four-component DiracKohnSham equation
to a two-component effective one-particle form by
means of a DouglasKroll transformation w 21, 22x .
In the scalar-relativistic version used in all calculations, spin-orbit interaction is neglected, resulting
in an effective one-component formalism.
In search of the ground-state structures, automatic geometry optimizations were performed using a quasi-Newton method. The structures of
excited states were determined by fixing the orbital occupation during the optimization procedure. With the aid of the counter poise method
w 23x , the basis set superposition error BSSE. of the
binding energy was estimated to 0.02 eV for the
ground state of Pd 2 ; the corresponding estimates
for ground states of Pd 4 are somewhat larger Td :
0.047 eV, D 2 d : 0.049 eV.. Since the latter examples
indicate only small variations of the BSSE for similar geometries, we refrained from correcting calculated cluster binding energies for the BSSE.

VOL. 74, NO 4

STRUCTURE OF SMALL Pd n SPECIES

Results and Discussion

PD ATOM
A prerequisite for the correct description of the
chemical bonding of TM compounds is a sufficiently accurate reproduction of the relative energies of various atomic configurations. Correlation
and relativistic effects are important in this respect. Therefore, we begin by examining experimental and calculated energies of various low-lying configurations of the Pd atom Table I.. To
facilitate comparison with calculated results, the
experimental values quoted were obtained by averaging over multiplet components of different
total angular momentum J, neglecting spin-orbit
interaction. As in most other studies, spherical
symmetry constraints were applied in all atomic
calculations, which lead to an upper bound of the
total energy of open-shell configurations of lower
symmetry.
Experimentally, the electronic ground state of
the Pd atom is 1S4 d 10 ., with the lowest triplet
state 3 D4 d 9 5s 1 . lying higher by 0.95 eV w 24x . Our
DF calculations correctly reproduce the 1 S4 d 10 .
ground state in both the nonrelativistic and the
relativistic case. The nonrelativistic calculation
yields a 1 S y3 D separation of 1.68 eV, overestimating the experimental value by 0.73 eV. When
scalar-relativistic effects are taken into account,
this single-triplet energy separation reduces to 0.99
eV, in very good agreement with experiment w 24x .

TABLE I
Comparison of nonrelativistic (nrel) and relativistic
(rel) GGA-BP relative energies of the low-lying
states of the Pd atom with experiment.a
Calc.
State

nrel

rel

Exp.b

D (4 d 9 5 s1)
D (4 d 9 5 s1)
3
P, 3 F (4 d 8 5 s 2 )

1.68
2.08 c
5.70

0.99
1.43 c
4.10

0.95
1.45
3.79 d

3
1

Energies (in eV) relative to the ground state 1S (4 d 10 ).

Ref. [24].
c
Average over multiplet components; see text.
d
Weighted configuration average with the energy of
3
F (4 d 8 5 s 2 ), 3.38 eV, taken from experiment, and the energy of 3 P (4 d 8 5 s 2 ), 4.76 eV, not available from experiment,
but estimated by means of SlaterCondon parameters [38].
b

This decrease of the d s excitation energy originates from the well-known stabilization of s orbitals and the destabilization of d orbitals due to
relativistic effects w 8x . Similar results have been
obtained in previous density functional calculations w 10, 19, 25x . With the LDA X functional, a
nonrelativistic value of 1.40 eV and a scalar-relativistic value of 0.73 eV have been calculated for
the singlet-triplet splitting w 19x , both being smaller
than the present generalized gradient approximation GGA. BP results. On the other hand, the
GGA BeckeLeeYangParr BLYP. functional w 26x
yields a scalar-relativistic singlet-triplet energy
separation of 0.98 eV w 25x close to the BP value.
The GGA-BLYP functional and the Becke threeparameters LYP hybrid functional B3LYP. w 27x in
conjunction with RECPs produce a slightly smaller
value, 0.87 eV w 10x , than the present all-electron
calculations. An extensive comparison of results
from different exchangecorrelation functionals is
available based on nonrelativistic calculations carried out with a double- valence plus polarization
DZVP. basis set w 12x . While the resulting BP value,
1.67 eV, agrees with the present results, small
deviations were obtained for other GGA functionals: 1.68 eV BPW91 w 28x. , 1.63 eV BLYP., and 1.51
eV PW86 w 29x. ; the hybrid functional B3LYP yields
1.51 eV w 12x . As this comparison shows, quite comparable results are to be expected if gradient-corrected functionals are employed. On the other
hand, it is mandatory to use an accurate basis set
as demonstrated by the same study w 12x . For a
large uncontracted, but too compact, basis set w 30x
the singlet-triplet separation is lowered by at least
0.5 eV, irrespective of the exchangecorrelation
functional applied. However, as the present comparison with more sophisticated relativistic calculations demonstrates, the resulting close agreement with experiment has to be considered as
fortuitous, at variance with previous conclusions
w 12x where these results have been used to declare
relativistic effects as unimportant for Pd species.
Comparison of results obtained by the HartreeFock HF. approach and increasing orders of
MllerPlesset MP. perturbation theory to account for correlation effects clearly demonstrates
the importance of electron correlation for an accurate description of low-lying states of the Pd atom.
At the nonrelativistic level, the 1 S y3 D energy
separation is calculated to 0.57 HF., 1.25 MP2.,
1.04 MP3., and 1.45 eV MP4. w 12x . An even smaller
HF value of 0.23 eV w 31x may be due to an insuffi-

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

407

XIAO ET AL.
cient basis set; it corresponds well to the result of
0.15 eV obtained with a basis set that is too compact w 12x . The corresponding scalar-relativistic and
nonrelativistic values from a numerical HF study
are 0.10 and 0.75 eV, respectively w 32x ; the relativistic effect of 0.65 eV on the singlet-triplet splitting is close to the present DF result of 0.69 eV,
which includes correlation effects.
The fact that a more sophisticated treatment of
electron correlation increases the calculated singlet-triplet separation is corroborated by results
from the quadratic configuration interaction QCI.
approach. When single and double excitations are
taken into account QCISD., a value of 1.15 eV is
calculated while perturbative treatment of triple
excitations w QCISDT.x yields 1.25 eV w 12x . The
singlet-triplet energy separation has also been calculated using the modified coupled pair functional
MCPF. w 33x where scalar-relativistic effects were
included via first-order perturbation theory. The
result of 0.88 eV is slightly lower than experiment
and the present scalar-relativistic DF result. The
same value of 0.88 eV has been obtained by means
of the multireference configuration interaction approach MRCI. w 34x .
For comparison, we also calculated the energies
of two higher-lying configurations, the singlet
4 d 9 5s 1 and the triplet 4 d 8 5s 2 . While the first configuration corresponds to the state 1 D, the second
configuration generates two states, 3 P and 3 F. Neither one of the state energies is directly accessible
within the present DF approach based on KS single-determinantal wave functions. If one neglects
orbital relaxation effects and interprets the DF total energy as an average over the underlying state
values w 3537x , one may compare calculated and
experimental values after suitable averaging. In
this approximation, one interprets the 4 d 9 5s 1 single-determinantal energy with m s s 0 as average
of the energy values of the 1 D and the 3 D m s s 0.
wave functions while the triplet energy of the
configuration 4 d 8 5s 2 has to be derived from a
weighted average of corresponding experimental
state energies. Since only the energy of 3 F 4 d 8 5s 2 .
is available from experiment, we estimated the
energy of 3 P 4 d 8 5s 2 . by means of SlaterCondon
parameters w 38x Table I.. Very good agreement is
found for the energy spacing of the 1 D state relative to the ground state 1 S when scalar-relativistic
effects are taken into account. Our estimated result
of 1.43 eV is considerably closer to experiment
1.45 eV w 24x. than the recent MRCI result of 1.19

408

eV w 34x . The larger discrepancy between calculated

and experimental excitation energies for the configuration 4 d 8 5s 2 shows that estimates of higher
excitation energies would require a more sophisticated approach e.g., time-dependent DF theory.
than the present simple DF procedure. However,
the discrepancy may in part be attributed to the
crude estimate of the experimental value of the
3
P 4 d 8 5s 2 . state energy Table I..
DIMER
In our examination of the Pd dimer, we concen.
trate on the characterization of the relativistic 3 q
u
. ground states and the
and nonrelativistic 1 q
g
1 q39, 40
..
states experimentally identified 3 q
u and u
3 q
1 q
2
1
1
While the states g u . and u u g . each can
be described by a single KS determinant, the 1 q
u
state of configuration u1g1 requires a description
by at least two determinants. The corresponding
singlet u1g1 KS solution is spin-contaminated,
representing at best an average of singlet and
triplet states similar to the case of the atomic state
1
D d 9 s 1 . discussed above. Thus, we estimated the
binding energy of 1 q
from suitable averages.
u
Since the other spectroscopic parameters obtained
for the singlet and triplet configurations u1g1 are
very similar Table II., the singlet results are expected to be a reasonable approximation to the
properties of the true 1 y
u state. Due to the many
possible excitations of d electrons, a variety of
other low-lying states exists, as demonstrated by
various theoretical studies w 31, 41, 42x .
Nonrelativistic and Relativisitc
GGA-BP Results
In the nonrelativistic case, we find a singlet
ground state 1 q
g for Pd 2 with a binding energy of
0.52 eV Table II.. Inclusion of scalar-relativistic
effects yields a strong change in the electronic
structure: The ground state changes to 3 q
u , in
agreement with experiment w 39, 40x , featuring a
considerably larger binding energy, 1.39 eV.
Since the nonrelativistic states lie close in energy, a change of the ground-state configuration
results from the fact that the configuration u1g1
undergoes a significantly different relativistic sta1 q
bilization 0.94 and 0.82 eV for 3 q
u ,
u and
respectively. than the nonrelativistic ground state
1 q
g 0.37 eV, Table II.. This change of states may
be rationalized with the aid of a Mulliken popula-

VOL. 74, NO 4

STRUCTURE OF SMALL Pd n SPECIES

small 5s contribution. The configuration u1g1 of
1 q
the states 3 q
u or u is formed by formally promoting one electron from 4 d to 5s, as shown by
the larger 5s populations. The relativistic stabilization of 5s orbitals consequently leads to a stronger
relativistic stabilization of these states with higher
s population. In other words, the relativistic reduction of the atomic excitation energy 4 d 10 4 d 9 5s 1
facilitates the occupation of the Pd 5s derived
bonding molecular orbital g of Pd 2 .
The different nature of the states considered is
also reflected in the spectroscopic parameters Ta1 q
ble II.. 3 q
u and u exhibit a short bond distance
which undergoes a relativistic contracof 2.55 A,
The state 1 qg features a considertion by 0.05 A.
which contracts
ably longer bond distance, 2.78 A,
The vibrational frequencies reflect the
by 0.08 A.
more shallow potential of the 4 d 10 dominated state
1 q
g compared to the other ones. While for 3 q
u or
1 q
u the calculated vibrational frequencies are
about 190 cmy1 and are shifted due to relativity to
207 and 204 cmy1 , respectively, 1 q
g exhibits a
vibrational frequency of 125 cmy1 , which increases
by 28 cmy1 if determined relativistically. Overall,
relativistic effects are quite important for an accurate description of Pd 2 and thus also for other Pd
compounds, at variance with the conclusions of
Ref. w 12x , as already noted previously w 911x .
Experimental data for Pd 2 are relatively scarce.
Dissociation energies of 0.73 " 0.26 w 43x , 1.13 "
0.22 w 43x , and 1.03 " 0.16 eV w 31x have been derived from experiments, where the last value is
regarded to be the most trustworthy one w 44x .
While our nonrelativistic value of 0.45 eV Table
II. considerably underestimates the triplet dissociation energy, the relativistically determined value
of 1.39 eV is closer to the experimental finding.
The photoelectron spectrum of Pd 2 shows two
strong electronic bands which were assigned to the
triplet ground state 3 q
u and a singlet excited state

TABLE II
Dissociation energy De (in eV), equilibrium bond
), and vibrational frequency e
length re (in A
(in cm y 1) for the low-lying states of Pd 2 and the
ground state of Pd 2y from nonrelativistic (nrel)
and relativistic (rel) GGA-BP calculations.
Calc.
State
De a

Pd 2

nrel

rel

Exp.

u+

0.45

1.39

u+
g+
3 +
u
1 +
u
1 +
g
3 +
u
1 +
u
1 +
g
2 +
u
2 +
u
2 +
u

0.17d
0.52
2.55
2.55
2.78
190
188
125
1.53
2.52
193

0.99d
0.89
2.50
2.50
2.70
207
204
156
2.36
2.47
215

0.73 " 0.26 b

1.13 " 0.22 b
1.03 " 0.16 c

1
1

re

Pd 2y

De f
re
e

210 " 10 e
200 " 15 e
2.15 " 0.17 e
206 " 15 e

Defined with respect to dissociation into two ground-state

Pd atoms (1S ).
b
Ref. [43].
c
Ref. [31].
d
Average over multiplet components; see text.
e
Refs. [39, 40].
f
Defined with respect to dissociation into a Pd atom and a
Pd y ion.

tion analysis Table III. and by recourse to the

relativistic effects on the relative energies of the
He configurations 4 d 10 and 4 d 9 5s 1 of the Pd atom
discussed above. The 5s population of the 1 q
g
state differs significantly from that of the states
3 q
2
u or 1 q
of state 1 q
u . The configuration u
g
describes predominantly the interaction of Pd
atoms of configuration 4 d 10 and exhibits only a
TABLE III

Mulliken populations per atom of the states 1 g+ , 3 u+ , and 1 u+ of Pd 2 and 2 u+ of Pd 2 y from nonrelativistic
(nrel) and relativistic (rel) GGA-BP calculations.
1

4d
5s
5p
a

g+

u+

u+a

u+

nrel

rel

nrel

rel

nrel

rel

nrel

rel

9.85
0.11
0.04

9.73
0.23
0.04

9.42
0.54
0.04

9.37
0.58
0.05

9.44
0.52
0.05

9.40
0.55
0.05

9.45
1.02
0.03

9.43
1.04
0.03

Derived from the calculated average over multiplet components; see text.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

409

XIAO ET AL.
w 39, 40x . According to experiment, excitation
q
u
1 q
w x
from 3 q
u to u requires 0.497 " 0.008 eV 39 .
The corresponding calculated excitation energy can
be derived from the difference of dissociation energies for various states as quoted in Table II. For the
1 q
excitation 3 q
u u our relativistic calculations
yield an estimate of 0.40 eV, in acceptable agreement with experiment. The photodetachment experiment on Pd 2 was not able to detect the state
1 q
g , which is assumed to lie close to the state 1 q
u
according to our GGA-BP results Table II.. The
vibrational frequencies derived in that experiment
y1 1 q
3 q
, u : 200 " 15 cmy1 . are in
u : 210 " 10 cm
very good agreement with our relativistic results
207 and 204 cmy1 , respectively; Table II.. The
experimental bond length difference between the
1 q
states 3 q
u and u was determined as negligible

0.007 A w 39, 40x. , in agreement with the present

calculations.
1

Comparison with other calculations

There are many other theoretical investigations
of Pd 2 based on a variety of methods w 9, 10, 12, 31,
33, 34, 41, 42, 4549x . However, a definite comparison is not always easy since quite often results are
only reported for the lowest singlet and triplet
states determined, leaving aside a full symmetry
classification.
We start by comparing to other nonrelativistic
calculations. In general they yield a singlet ground
state, independent of the details of the method w 9,
10, 12, 31, 49x . However, as in our density functional calculations, the lowest triplet state is found
to be close to the ground state Table II.. All-electron DF calculations employing the same GGA-BP
functional as the present work yielded binding
energies for the singlet ground state of 0.56 eV w 9x
and 0.57 eV w 49x , in close agreement with our
result 0.52 eV.. These studies found the lowest
triplet state almost degenerate with the ground
state, with an energy separation of less than 0.05
eV w 9, 49x , comparable to our result of 0.07 eV
Table II.. Application of a nonrelativistic pseudopotential in a BP calculation lead to a slight
lowering of the binding energies singlet: 0.47 eV,
triplet: 0.51 eV. and an inversion of states w 9x . The
lower binding energies with pseudopotential techniques may be due to the missing relaxation of the
core electrons. Concomitant with the well-known
tendency of LDA to overestimate binding energies,
the binding energies of both the singlet and the
triplet state are calculated with LDA by up to 0.5

410

eV larger w 9x . As in the case of GGA calculations,

the LDA binding energy value is reduced when
pseudopotentials are employed w 9x . Different nonrelativistic results have been obtained from conventional quantum chemical methods. In an earlier
limited singlesdoubles CI SDCI. calculation w 31x
a 1 q
g ground state was determined, but it was
found to lie 0.74 eV above the separated-atom
limit. An MP4 calculation MP4SDTQ. found a
stable singlet 0.17 eV. but no stable triplet w 12x .
Previous nonrelativistic DF calculations yielded
a bond length of the singlet ground state of Pd 2 of
by GGA-BP and 2.70 A
by LDA and
about 2.80 A
GGA-BLYP w 9, 10, 49x , while the triplet state was
found to exhibit a considerably shorter bond, by
w 9, 10, 49x , independent of the compu0.200.25 A
tational method applied. All these DF results are
in good agreement with the result of the present
work Table II.. Conventional quantum chemistry
results deviate again. A limited SDCI calculation
both for the
determined a bond distance of 2.80 A,
singlet and the triplet state w 31x . The MP4SDTQ
approach w 12x furnishes a relatively long distance
for the singlet, but a triplet value, 2.49 A,

of 3.11 A
that is slightly shorter than the corresponding DF
values. Harmonic vibrational frequencies from
nonrelativistic DF calculations are consistent with
the bond lengths: The singlet state exhibits a longer
interatomic distance and thus a lower frequency
than the triplet state. GGA-BP calculations yield
about 123 cmy1 for the singlet and 185 cmy1 for
the lowest triplet state w 9, 49x , in agreement with
the present work. LDA calculations w 9x lead to
slightly higher frequencies singlet: 147 cmy1 ,
triplet: 210 cmy1 .. The only nonrelativistic CI determination of vibrational frequencies w 31x resulted
in a value of 132 cmy1 for the singlet ground state,
in agreement with the DF results. For the lowest
triplet, on the other hand, a very low value of 134
cmy1 was obtained, concomitant with the overestimation of the bond length see above.. Overall,
consistent nonrelativistic results have been
achieved by different DF approaches while the few
conventional quantum chemical results deviate
from them in some notable aspects.
Now we turn to a comparison with previously
reported relativistic studies of Pd 2 . All of them
applied pseudopotentials to account for relativistic
effects, whether carried out with DF w 9, 10, 42, 47,
49x or conventional quantum chemical methods
multireference, singlesdoubles CI, MRSDCI w 41x ,
complete active space method with second-order

VOL. 74, NO 4

STRUCTURE OF SMALL Pd n SPECIES

perturbation theory, CASPT2 w 42x , MCPF w 33x. . In
line with our DF work, a triplet ground state was
found with all approaches. A difficulty arises for
the comparison of the singlet results. As discussed
1 1 . are
above, our results for the state 1 q
u u g
estimates only. On the other hand, our results for
2 . Table II., which is almost dethe state 1 q
g u
1 1.
generate with the state 1 q
u u g , are comparable
to those of the lowest singlet state of other
investigations which do not specify the spatial
symmetry of the state. Therefore, we shall base our
comparison of the relativistic lowest singlet state
of other investigations on our results of the state
1 q
g . The assumption that 1 q
g may be the lowest
singlet state of Pd 2 is confirmed by MRCI calculations which find this state by 0.42 w 41x or 0.23 eV
w 34x below 1 q
u . With the less accurate CASPT2
1 q
w x
approach, 1 q
g is calculated 0.02 eV above u 42 ;
1 q
according to our estimate, g is by 0.1 eV weaker
Table II.. As already mentioned
bound than 1 q
u
above, our estimate of 0.40 eV for the excitation
3 q
u 1 q
u is in fair agreement with experiment
0.50 eV w 39x. . An MRSDCI w 41x and a CASPT2 w 42x
calculation found a higher value of 0.56 eV while a
lower result of 0.33 eV was obtained in another
MRCI study w 34x .
After discussion of the few unambiguous results available for the state 1 q
u , we will assume in
the following the lowest singlet state of Pd 2 to be
the state 1 q
g . Relativistic GGA-BP and hybrid DF
B3LYP. calculations yield a triplet ground-state
binding energy of 0.91.05 eV and a triplet-singlet
separation of 0.30.45 eV w 9, 10, 42, 49x . Both quantities are lower than the results of our all-electron
calculation 1.39 and 0.50 eV; Table II.. These previous DF triplet binding energies w 9, 10, 42, 49x are
in good agreement with experiment about 1.03 "
0.16 eV w 31x. , yet this lower value compared to the
result of the present GGA-BP study may be due to
the use of RECPs see above.. Higher ground-state
binding energies of about 1.3 eV are obtained in
self-consistent LDA calculations w 9, 10, 47x . It is
somewhat surprising that a very similar value is
obtained from a postself-consistent field postSCF. procedure where a GGA functional BLYP,
PerdewPerdew w 18, 50x. is evaluated for the LDA
electron density w 10, 47x . LDA values for the
triplet-singlet separation, on the other hand, agree
with those of the GGA studies mentioned above
0.30.4 eV.. The DF-RECP results for the bond
length of Pd 2 are in agreement with the trends
discussed for the binding energies. GGA studies

w 9, 10, 42, 49x yield slightly longer distances

. for the ground state than the present
2.532.54 A
.. The same trend is observed
calculation 2.50 A
for the lowest singlet state; DF-RECP calculations
while the present all-electron
furnish 2.742.77 A,
Table II.. In line with the
approach yields 2.70 A
higher binding energies, the LDA leads to a shorter
. as
bond length for the lowest singlet 2.442.48 A
. w 9, 10, 47x .
well as for the triplet state 2.612.68 A
Also, the vibrational frequencies follow these
trends. Our values are slightly higher than GGABP-RECP results w 9, 49x and more similar to LDARECP values w 9, 10, 47x .
Just as for the nonrelativistic calculations, there
are considerable differences between relativistic density functional and conventional quantum
chemical studies of Pd 2 . A CASPT2 study w 42x as
well as a MRSDCI calculation w 41x both with
RECP. yield binding energies of the ground state
3 q
u in line with the GGA-RECP results discussed
above, 0.98 eV w 42x and 0.85 eV w 41x , respectively.
Different results were obtained for the energy separation from the ground-state triplet to the singlet
1 q
g . The CASPT2 value of 0.58 eV compares well
.
with our result of 0.50 eV for 1 q
g ; Table II while
the MRSDCI approach, more accurate in principle,
leads to a very low value of 0.14 eV w 41x , which is
close the result of another MRCI study 0.10 eV
w 34x. . Both conventional post-HF methods yield
bond lengths shorter than the GGA results for the
ground state. With the CASPT2 method w 42x the
of the ground state
relatively short result of 2.43 A
in the lowest singlet state, a
increases by 0.12 A
change that is only about half as large as in DF
determined
calculations. The bond length of 2.48 A
by means of the MRSDCI method w 41x is only
slightly smaller than the present GGA-BP result,
On the other hand, the increase of the bond
2.50 A.
distance in the singlet state is calculated larger,
than with any other method that includes
0.39 A,
relativistic effects. The vibrational frequencies determined with the MRSDCI method w 41x triplet:
160 cmy1 ; singlet: 121 cmy1 . are somewhat smaller
than those of the current DF calculation which
agree well with available experimental data. A
lower triplet ground-state binding energy has been
obtained by the averaged coupled pair functional
ACPF. method 0.74 eV. w 33x .
Finally, we turn to a comparison of the relativistic effects on the various properties of Pd 2 . A
direct comparison of the present all-electron DF
results is only possible with the results of a pseu-

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411

XIAO ET AL.
dopotential LDA and GGA study w 9x since this is
the only other work where nonrelativistic and relativistic calculations were performed with the same
methodology. The relativistic effects of our allelectron gradient-corrected DF calculation are
larger than those of the pseudopotential LDA results, but they exhibit the same trends. The LDA
binding energy increases by 0.80 eV for the triplet
ground state and by 0.29 eV for the singlet state;
these values are only slightly smaller than our
results of 0.94 and 0.37 eV, respectively Table II..
The relativistic contraction of the bond length has
for the triplet
been found noticeably smaller, 0.02 A
for the singlet state, compared to our
and 0.05 A

all-electron results of 0.05 triplet. and 0.08 A

singlet.. The corresponding changes of the vibrational frequency are in line with these trends: the
LDA pseudopotential approach leads to relativistic
blue shifts that are by about 10 cmy1 smaller than
those of the present all-electron GGA-BP calculation. On the other hand, the corresponding GGARECP results w 9x deviate considerably from those
of our calculations, although the same GGA exchangecorrelation functional BP. was applied.
The relativistic stabilization of the Pd 2 bond was
found significantly smaller triplet: 0.38 eV; singlet: 0.12 eV w 9x. . Instead of the expected contraction, that relativistic calculation yielded elonga in the triplet
tions !. of the bond length by 0.02 A
in the singlet state. This is a highly
and by 0.03 A
unusual result, at variance with physical expectation w 8x . Despite this relativistic lengthening of the
Pd 2 bond, relativistic blue shifts were calculated
for the vibrational frequency, q43 and q29 cmy1
for the lowest triplet and singlet states, respectively. These frequency shifts are comparable or
larger than the ones obtained in our all-electron
calculations triplet: q17 cmy1 , singlet: q31 cmy1 ;
Table II. although a considerably smaller increase
of the binding energy was observed see above..
These relatively strong deviations from the relativistic effects obtained by our all-electron calculation demonstrate a clear limitation of the pseudopotential approach for such a sensitive bond as
that of the Pd dimer. In particular, a relativistic
elongation of the Pd 2 bond seems to be an obvious
methodological artifact, given the fact that s orbitals play an important role see above.. This
latter conclusion is corroborated by the LDA results of that same study w 9x .

412

DIMER ANION
As further confirmation of the quality of our
computational approach, we also examined the
anion Pd 2y for which experimental information is
available w 30, 49x . Moreover, Pd 2y is an interesting
molecule by itself. In particular, anions may present special problems to an approximate DF
method due to incomplete cancellation of self-interaction w 51x . These problems may be enhanced if
localized basis sets are employed to represent the
KS orbitals since orbitals of positive energy may
have to be occupied w 52, 53x . Such a situation is
encountered for Pd 2y where the energy of the u
orbital is q0.51 eV for the nonrelativistic case. We
are well aware of the ensuing theoretical problems
w 51x ; tests with substantially enlarged basis sets
lowered the orbital energy but did not render it
negative. Nevertheless, we will compare our results with experiment to explore the practicability
of a DF approach even in such a case. Our relativistic as well as nonrelativistic BP calculations
Table II. yield 2 q
g2u1 . as ground state, in
u
agreement with experiment w 39, 40x . The experimental dissociation energy of 2.15 " 0.17 eV is
only reproduced by the scalar-relativistic level of
theory, which yields 2.36 eV. As for the neutral
dimer, this relativistic value is in considerably
better agreement with experiment than the corresponding nonrelativistic result of 1.53 eV, but it
exceeds the experimental value slightly. Experimentally, the energy difference between Pd 2 and
Pd 2y, 1.123 " 0.013 eV w 39x , has been determined
more accurately than the absolute dissociation energy; this energy difference is well reproduced by
our calculation 0.97 eV, Table II.. Note that the
dimer anion features a stronger bond than the
neutral parent molecule. This can be traced to the
fact that the extra electron occupies a bonding g
orbital. The character of this orbital, which is independent of relativistic effects, has already been
analyzed; see the above discussion of the state 3 q
u
g1u1 . of Pd 2 Table III.. As expected, the bond
length of the Pd 2 anion is shorter than that of the
neutral dimer due to the stronger bond Table II..
At the nonrelativistic and relativistic levels of the respectively,
ory, contractions of 0.025 and 0.035 A,
relative to Pd 2 were calculated. The latter finding
is in very good agreement with the experimentally
determined bond length difference of 0.037 " 0.008
w 39x . Also for the vibrational frequency a quite
A
accurate result was obtained. The calculated rela-

VOL. 74, NO 4

STRUCTURE OF SMALL Pd n SPECIES

tivistic value of 215 cmy1 is close to the measured
frequency of 206 " 15 cmy1 w 39x . Although the
bond of the anion is considerably strengthened,
the rather small contraction of the bond length and
the minor change in the calculated vibrational frequency compared to the neutral molecule point
toward a shallow potential curve.

TABLE IV

) of low-lying states
Optimized bond lengths (in A
of the cluster Pd 4 for various geometries from
nonrelativistic (nrel) and relativistic (rel)
GGA-BP calculations.
Symmetry
Td
D 2d

TETRAMER
To determine the ground-state geometry and to
examine the influence of relativistic effects, we
consider various structures of Pd 4 . Starting from
the tetrahedral geometry point group Td ., a search
for possible distortions was undertaken by employing various symmetry constraints D 2 d , C2 v ,
and C3 v .. For comparison and as reference for
adsorption complexes w 54x also a square-planar
structure D4 h . was inspected as well as distortions into rectangular and rhombic shapes D 2 h ..
The results of these geometry optimizations are
collected in Tables IV and V. We start the discussion with the geometrical aspects based on the
scalar-relativistic results. Relativistic effects will
then be considered by comparison with the corresponding nonrelativistic calculations.
Relativistic structure optimization of Pd 4 in tetrahedral geometry leads to a 3 T1 ground state of
configuration t 14 with a total binding energy of
The
6.62 eV and a PdPd bond length of 2.61 A.
.
metalmetal bond is longer than for Pd 2 2.50 A
but shorter than the bulk interatomic distance of
w 55x , as expected on the basis of the
Pd of 2.75 A
intermediate effective coordination w 3, 7x . Since the
ground state exhibits an open-shell structure, the
energy may be lowered by a JahnTeller distortion.
We followed two possible routes of symmetry
reduction. Distortion from Td to D 2 d symmetry
deforms the tetrahedron into two perpendicularly
oriented dimers with two equivalent intradimer
bond distances r 1 and r 2 and four equivalent
interdimer bonds r 3 . With a D 2 d symmetry constraint, the ground state 3 T1 of Pd 4 Td . splits into
the states 3A 2 and 3 E, with the former being the
D 2 d ground state. The corresponding gain in binding energy relative to the Td ground state is 0.04
eV only. The accompanying geometric distortions
are more noteworthy since the two intradimer
while r 3 is elongated to
bonds shorten to 2.56 A,
Distortions of opposite sign are found for
2.64 A.

State
3
3

T1
A2

A2

B1

B2

C 3v

A2

D4h
D2 h

C 2v

A 1g
Ag

Bond
lengths a

nrel

rel

r1 = r 2 = r 3
r1 = r 2
r3
r1 = r 2
r3
r1 = r 2
r3
r1
r2
r3
r1
r2
r3
r1
r2
r
r1
r2

2.67
2.62
2.70
2.71
2.65
2.62
2.70
2.79
2.62
2.66
2.62
2.79
2.66
2.61
2.74
2.54
2.51
2.65

2.61
2.56
2.64
2.65
2.60
2.57
2.63
2.72
2.57
2.60
2.57
2.72
2.60
2.56
2.68
2.49
2.47
2.59

D 2 d , C 2 v : r1 , r 2 the two horizontally oriented edges (dimers); r 3 the four equivalent bonds connecting the two
horizontally oriented edges. C 3 v : r1 the edge of the equilateral base triangle; r 2 edge from the base atoms to the
capping atom. D4 h : redge of the square. D 2 h : rhombic
shape, r1 short axis of the rhombus; r 2 edge of the
rhombus.

the state 3 E, which is stabilized even less, by only

0.01 eV. Here, the intradimer bond distance elon and r 3 is contracted by 0.01 A

gates by 0.04 A,
compared to the tetrahedral structure. Since the
D 2 d ground state with configuration e 2 a22 exhibits
a closed shell highest occupied molecular orbital
HOMO. a 2 ., no further symmetry reduction is
expected. Optimization of Pd 4 in C2 v symmetry,
which allows the bond r 1 and r 2 to be different,
neither lead to a symmetry lowering nor to a
geometric distortion Table IV.. Under C2 v symmetry constraint slightly different results by up to
. were obtained for the two bond lengths
0.01 A
r 1 s r 2 and r 3 of the D 2 d geometry Table IV..
These differences could be traced to different orientations of the integration grid; with a more accurate integration grid these artifacts were reduced
For the close lying 3 E state, on
to less than 0.002 A.
the other hand, the configuration of e 3 a 22 allows a

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

413

XIAO ET AL.
TABLE V
Dissociation energy De (in eV) of low-lying states of
the cluster Pd 4 with Td , D 2 d , C 2 v , C 3 v , D4 h , and D 2 h
symmetry from nonrelativistic (nrel) and relativistic
(rel) GGA-BP calculations.
Dea
Symmetry

State

Td
D 2d

T1
A2
3
E
3
A2
3
B1
3
B2
3
A2
1
A 1g
1
Ag

C 2v

C 3v
D4h
D 2 hb

nrel

rel

4.17
4.21
4.19
4.21
4.20
4.20
4.18
3.52
3.38

6.62
6.66
6.63
6.66
6.66
6.66
6.63
5.95
5.74

a
Defined with respect to four Pd atoms in the ground state
(1S).
b
Rhombic shape.

JahnTeller distortion, implying a splitting of the

HOMO e. In C2 v symmetry, the 3 E state splits into
the two degenerate states 3 B1 and 3 B2 which are
each stabilized by only about 0.01 eV relative to 3 E.
Nevertheless, the geometry relaxes considerably.
are
The interdimer bond lengths r 3 of 2.60 A
preserved, but the intradimer bonds r 1 and r 2
which correexhibit distances of 2.57 and 2.72 A

spond to a contraction by 0.08 A and an elongation

respectively, compared to the state 3 E
by 0.07 A,
D 2 d ..
An alternative route of symmetry lowering of
the tetrahedron preserves one threefold axis C3 v ..
As in the case of D 2 d , the 3 T1 ground state splits
into the states 3A 2 and 3 E. The binding energy of
the ground state 3A 2 increases less than for the D 2 d
distortion, by 0.01 eV only. The bond length of the

equilateral triangle base is shortened by 0.05 A

relative to the Td geometry, while the bonds to the
Tacapping fourth atom are elongated by 0.07 A
ble IV.. As for the other geometries, the intermetallic bond appears to be rather soft, allowing strong
geometrical changes despite marginal variations of
the total energy.
As a further possible geometry of Pd 4 , we examined planar structures in comparison to the
three-dimensional arrangements discussed above.
In square-planar geometry D4 h . Pd 4 exhibits a
closed-shell ground state, 1A1 g , which prevents
JahnTeller distortions to rectangular or rhombic
structures. With a binding energy of 5.95 eV, this

414

geometry is by 0.7 eV less stable than the tetrahe Table

dron Table V.. The bond distance of 2.49 A
IV. is comparable to the Pd dimer and considerably shorter than for the tetrahedral geometry 2.61
., which can be rationalized by lower effective
A
coordination w 3, 7x . Although the square-planar
cluster isomer is stable with respect to distortions
of D 2 h symmetry, a Pd 4 species with rhombic
structure was found. In this geometry Table IV.,
the short axis of the rhombus represents the short which is even
est PdPd bond distance, 2.47 A,
Since
shorter than the dimer bond distance, 2.50 A.
the edge length of the rhombus is considerably
this geometry can be viewed as a
longer, 2.59 A,
dimer with two attached atoms. This rhombic
structure is calculated to be less stable by 0.21 eV
than the square-planar geometry.
Comparison of our relativistic and nonrelativistic binding energies Table V. reveals a very uniform increase due to relativistic effects by about
2.45 eV for all geometries and states of Pd 4 considered. This is no surprise for the D 2 d , C2 v , and C3 v
structures since all states are derived from the 3 T1
ground state of tetrahedral Pd 4 and thus should
exhibit a similar bonding character. The relativistic
strengthening of the PdPd bond for the planar
geometries is also of similar size. Inspection of the
atomic effective configuration in Pd 4 in its various
geometries reveals no substantial differences. For
the ground state of Td symmetry a Mulliken population analysis of the nonrelativistic orbitals yields
an effective atomic configuration s 0.56 p 0.09 d 9.35 ; in
the relativistic case the s character increases only
slightly s 0.61 p 0.10 d 9.29 .. The deviations for other
geometries and states are always less than 0.05.
The above effective configuration is very similar to
the one determined for the ground state of Pd 2
Table III.; also the binding energy per bond is
comparable, about 1.1 eV including relativistic effects. In line with the above observations, also the
relativistic contraction of the bond length is quite

uniform in all cases considered, y0.06 " 0.01 A

Table IV.. As a consequence of the very similar
effect of relativity on all species examined, the
discussion of structure and bonding of the relativistic results applies also to the corresponding
nonrelativistic cases. Nevertheless, a relativistic
treatment is mandatory to achieve quantitative
results, especially for the binding energy.
To the best of our knowledge, there are no
experimental data available for Pd 4 . Compared to
Pd 2 also theoretical studies are less numerous. In a

VOL. 74, NO 4

STRUCTURE OF SMALL Pd n SPECIES

DF-RECP optimization of Pd 4 using the hybrid
B3LYP approach w 10x , a C2 v distorted geometry
was obtained with a 3 B2 ground state. As shown
above, this state is almost degenerate with the 3A 2
ground state of D 2 d symmetry Table V., and
slight methodological differences may thus easily
lead to a reordering of states. The bond lengths
for r1 and r 2 and 2.64
determined, 2.60 and 2.78 A

A for r 3 , are in agreement with the present calculation Table IV.. The corresponding distances are
slightly longer than the present relativistic results
and, although obtained with a relativistic pseudopotential, they are more similar to our nonrelativistic values. That same trend was already observed for Pd 2 see above.. Preference of three-dimensional structures compared to planar ones was
also derived from other first principles w 56x as well
as from semiempirical studies w 48, 57x . With the
MRSDCI method using RECPs. various planar
geometries have been compared to the tetrahedral
one w 56x . The Td geometry was found to be the
most stable with a 3 T1 ground state in agreement
with the present DF results. The total binding
energy was calculated about 1 eV smaller than the
GGA-BP value of the present study. This finding is

in line with the calculated bond length of 2.69 A,

which is even longer than our nonrelativistic result. The results for the square-planar geometry
follow the same trends w 56x . Interestingly, a rhombic planar geometry was found to be by 0.46 eV
more stable than a square-planar structure, at variance with the present work, which yields the
square-planar geometry slightly more stable Table
V.. Also the shape of the rhombus is quite differ and
ent cf. Table IV.: with a short axis of 2.70 A
both PdPd distances are
an edge length of 2.67 A
very similar, although the same ground state 1A g
as in the present calculation was determined w 56x .
according to the
The two distances differ by 0.12 A
present scalar-relativistic calculations see above..
surmounting
Bond lengths of more than 2.8 A,
.
even the interatomic distance of bulk Pd 2.75 A
resulted from the less accurate CASSCF approach
w 56x for various geometries of the Pd 4 cluster.
Geometry optimizations performed with a modified extended Huckel
method w 57x determined the

in very
bond length of the tetrahedron to 2.59 A
good agreement with our relativistic result of 2.61
Table IV.. On the other hand, the difference of
A
the nonequivalent bond lengths of the C3 v geome Table IV. is considerably underestitry 0.12 A;

mated by this simple molecular orbital approach

only.
where it is calculated to 0.01 A
Summarizing the discussion, we find that in
agreement with other studies w 48, 56, 57x three-dimensional geometric arrangements of a Pd 4 cluster are clearly preferred. Due to the very small
energy differences of the various structures examined, a definite determination of the ground-state
geometry is not possible. A distortion of the tetrahedral geometry is very likely due to the spatially
degenerate open-shell electronic structure of that
state. Besides the D 2 d and C3 v isomers found in
this work, even a further symmetry reduction to
C2 v cannot be excluded due to very low lying
excited open-shell states. Thus, the structure of
Pd 4 has to be regarded as quite flexible and
changes between various isomers of three-dimensional structure should be easily feasible.

Conclusions
For the first time, consistent all-electron density
functional calculations using a gradient-corrected
exchangecorrelation functional have been carried
out to examine the influence of relativistic effects
on small Pd n n s 1, 2, 4. species as well as on
Pd 2y. Relativistic effects were found to considerably improve agreement between experimental and
calculated values of the energy separation of low
lying states of a Pd atom. For molecular species
relativistic effects cause a slight contraction of the
bond lengths, an increase of the vibrational frequency, and a significant enhancement of the binding energy. In line with other theoretical studies a
change of the ground state of Pd 2 from singlet to
triplet was found due to a differential relativistic
effect. Comparison with available experimental
data yields good agreement, especially for the vibrational frequencies of Pd 2 and its anion, while
binding energies are calculated slightly too large.
Small systematic deviations were found between
the all-electron results and those of comparable
pseudopotential calculations lower binding energies and smaller relativistic effects.; these differences are very likely due to a missing polarization
of the core shells. Differences in spectroscopic parameters between the dimer and its anion are well
reproduced by the present relativistic calculations.
For Pd 4 , three-dimensional structures are clearly
preferred over two-dimensional ones. Geometries
of Td , D 2 d , and C3 v symmetry were found to be
energetically almost degenerate. Thus, while the

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

415

XIAO ET AL.
present calculations yield the minimum energy at
a D 2 d structure, a definite conclusion concerning
the ground-state geometry of Pd 4 cannot be drawn.
ACKNOWLEDGMENT
One of us C.X.. thanks the Alexander von
Humboldt Foundation for a fellowship. This work
was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.

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