Molecular density functional calculations in the regular relativistic approximation:

Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and
comparison with first-order relativistic calculations
Christoph van Wüllen

Citation: The Journal of Chemical Physics 109, 392 (1998); doi: 10.1063/1.476576
View online: http://dx.doi.org/10.1063/1.476576
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 JOURNAL OF CHEMICAL PHYSICS VOLUME 109, NUMBER 2 8 JULY 1998

Molecular density functional calculations in the regular relativistic

approximation: Method, application to coinage metal diatomics,
hydrides, fluorides and chlorides, and comparison with first-order
relativistic calculations
Christoph van Wüllen
Lehrstuhl für Theoretische Chemie, Ruhr-Universität, D-44780 Bochum, Germany
~Received 3 February 1998; accepted 31 March 1998!
The application of the zeroth-order regular relativistic approximation ~ZORA! for molecular density
functional calculations is investigated. By introducing a model potential to construct the kinetic
energy operator, stationarity of the energy with respect to orbital variations is gained and most
problems connected with gauge dependence of the regular approximation are eliminated. The
formulation of a geometry gradient is greatly facilitated using this formalism. Calculations for the
coinage metal hydrides ~CuH, AgH, AuH! as well as for the homonuclear ~Cu2, Ag2, Au2! and
heteronuclear ~CuAg, CuAu, AgAu! diatomics show that the results of ZORA calculations within
the electrostatic shift approximation, as introduced by van Lenthe and co-workers, can be duplicated
using the simpler scheme proposed in this work. Results for the coinage metal fluorides ~CuF, AgF,
AuF! and chlorides ~CuCl, AgCl, AuCl! are presented as well. First-order relativistic calculations
have been performed for all systems to assess the applicability of leading-order relativistic
perturbation theory. © 1998 American Institute of Physics. @S0021-9606~98!30226-3#

I. INTRODUCTION tries to circumvent a fundamental problem of the ZORA

Recently, Baerends, van Lenthe, and co-workers1–3 have
discussed two-component computational schemes for ap-
proximately solving Dirac’s equation that are variationally
stable in Coulomb fields ~i.e., in atoms and molecules!.
These schemes can be rationalized as a perturbational expan-
sion of Dirac’s equation.4 To the lowest order, termed ZORA
~zeroth-order regular approximation!, one obtains a Hamil-
tonian which already includes relativistic effects and which
turned out to be identical to the one derived earlier by
Chang, Pélissier, and Durand5 ~‘‘CPD Hamiltonian’’! in a
different context. For hydrogenlike systems, exact solutions
of the ZORA equation ~i.e., eigenfunctions of the CPD
Hamiltonian! have been calculated6 and found to be the best
possible two-component approximation to the fully relativis-
tic wave function. Most applications of the ZORA equation
for many-electron systems have been done in the context of
Kohn–Sham density functional calculations, both at a scalar-
relativistic level2 and with the consideration of spin-orbit
effects.3 However, the method has largely been restricted to
atoms and diatomic molecules, and, for reasons to be dis-
cussed below, little is known about the performance of
ZORA to polyatomic molecules where one can do little work
without having analytical geometry gradients available. Note
that there exist applications of ZORA for larger, namely pe-
riodic systems.7 In that work, geometry gradients were also
not available and therefore only one degree of freedom could
be investigated.
In the molecular ZORA calculations presented so far,
the evaluation of energy differences is somewhat cumber-
some. The procedure presented by van Lenthe and co-
workers, called the electrostatic shift approximation ~ESA!,2
equation, namely that it is not gauge invariant. This means
that changes in the electronic Coulomb and exchange-
correlation potentials, as occurring when forming chemical
bonds or ionizing a system, do not have the correct effect on
the ZORA energy levels. Given further that in the many-
electron case the ZORA energy is not stationary with respect
to orbital variations, it is perhaps not surprising that analyti-
cal geometry gradients are not yet available for this method.
In this article, a modification of the ZORA approach
~within the Kohn–Sham density functional scheme! is pre-
sented that eliminates both problems ~gauge noninvariance
and nonstationarity of the energy! mentioned above. This is
accomplished using a model potential ~that does not depend
on the actual electron density! to construct the ZORA kinetic
energy operator. Then, the formulation of an analytical ge-
ometry gradient is almost a trivial problem. This method is
called ZORA~MP! ~MP stands for model potential! and will
be outlined in Sec. II. In Sec. III computational aspects are
discussed, especially the basis set generation, the accuracy of
the numerical quadrature and the construction of the model
potential. The results are discussed in Sec. IV. In a first series
of calculations, it is established by comparison with the ZO-
RA~ESA! results that the modified procedure is a valid ap-
proximation. Then, some new results for the coinage metal
fluorides and chlorides are given.
II. ZORA KOHN–SHAM METHOD
The ZORA ~or CPD! Hamiltonian reads
Ĥ ZORA5Ĥ ZORA1V ~1!
with

0021-9606/98/109(2)/392/8/$15.00 392 © 1998 American Institute of Physics

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 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998
T̂ ZORA5 spv ~ r ! sp,
c2
v ~ r! 5 .
2c 2 2V ~ r!
Here, s5( s x , s y , s z ) is the vector of the Pauli spin matri-
ces, p52i“ the momentum operator ~in atomic units!, and
c the velocity of light in atomic units, which is the inverse of
the fine structure constant. The function v (r) is zero at the
position of the nuclei, where the potential goes to minus
infinity. In the valence region, where the absolute value of V
is small compared to c 2 ,
1 V~ r !
v ~ r! 5 1 1O ~ c 24 ! .
2 4c 2
In many-electron Kohn–Sham calculations, Ĥ ZORA enters the
one-particle equations, and here the potential V(r) includes
the external potential ~nuclear attraction!, the electronic
~electrostatic! Coulomb potential and the exchange-
correlation potential:
~ T̂ ZORA1V ! w i 5 e i w i ,
V5V N 1V C 1V XC .
The electronic Coulomb and exchange-correlation potentials
are calculated from the electron density which can be calcu-
lated by the nonrelativistic formula1,2
(i w *i ~ r ! w i~ r! .
r ~ r! 5
We will always use nonrelativistic exchange-correlation
functionals, i.e., neglect magnetic effects and retardation in
the electron interaction. This roughly corresponds to the use
of the Dirac–Coulomb operator in ab initio calculations. For
density functional calculations, it has been shown that this
introduces only small errors as long as valence properties
such as bond lengths, binding energies and vibrational fre-
quencies are considered.8 The Kohn–Sham electronic energy
thus reads
E5 (i ^ w iu T̂ ZORAu w i & 1 E r ~ r! V ext~ r! dr
Er
1 ~ r1 ! r ~ r2 !
1 dr1E XC ~ r ~ r!! .
2 r 12
In general, the exchange-correlation energy E XC will not
only depend on the electron density, but also on the spin
density ~or, better, on the spin magnetization!. In this case,
the exchange-correlation potential is spin-dependent. Since
T̂ ZORA depends ~via V C and V XC ! on the Kohn–Sham orbit-
als w i , the total energy is not stationary with respect to or-
bital variations. Other known problems of the ZORA ap-
proach are also connected with the fact that T̂ ZORA depends
on the orbitals: If one removes a valence electron from an
atom ~or molecule!, this results in a nearly constant shift of
the Coulomb potential in the atomic core. However, the en-
ergy levels of the deep core orbitals are not shifted by this
constant ~what they should! since the ZORA equation is not
gauge invariant.2 It is therefore not possible to evaluate ion-
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Christoph van Wüllen 393
ization energies by simply taking the difference in total en-
~2! ergy between the atom and the ion ~this is illustrated in Sec.
IV!. Similar considerations apply to the evaluation of mo-
lecular binding energies since bond formation also results in
a potential shift in the core region ~the ESCA shift!. For the
same reason, the ZORA method will give wrong intermo-
lecular forces if one of the fragments is charged. Possible
ways to eliminate these problems are the inclusion of higher
orders in the perturbative treatment or a scaling of the
Kohn–Sham orbital eigenvalues.2 However, formulating gra-
dients for these methods seems even more involved.
If it is accepted that the dependence of T̂ ZORA on the
Kohn–Sham orbitals is the origin of the problems, one might
~3!
wonder if V C and V XC could simply be neglected in T̂ ZORA .
One could argue that the relativistic effect on bond lengths,
binding energies, etc., is to a large extent a one-electron ef-
fect. For example, in first-order relativistic calculations based
on the Pauli operator, valence properties are not much af-
fected by the two-electron Darwin term.9 Furthermore, to
reproduce the essential features of the function v (r) @Eq.
~2!#, especially its behavior close to the nuclei, it is sufficient
~4! only to regard the nuclear attraction potential when con-
structing v (r). However, consider two neutral molecules, A
and B, at a large distance. The nuclei of A will induce a
constant shift of the potential in the region of B ~and vice
versa!. This shift has no effect in gauge invariant theories but
leads to an unphysical force in ZORA calculations. So one
must include at least the electrostatic Coulomb potential in
~5!
v (r) to cancel the long-range tails of the nuclear attraction.
The idea is now to use a model potential Ṽ(r) to construct
v (r) and hence the operator T̂ ZORA . Ṽ(r) should have the
following properties:
~1! v (r) has the correct behavior near the nuclei;
~2! Ṽ(r) does not depend on the Kohn–Sham orbitals;
~3! Ṽ(r) has no contribution from distant atoms or mol-
ecules;
~4! a smooth analytical expression is available for Ṽ(r).
Property ~2! ensures that the total energy is stationary with
respect to orbital variations and, since the model potential
Ṽ(r) depends on the molecular geometry alone, this will
facilitate gradient calculations. Moreover, the matrix ele-
~6! ments of T̂ ZORA need only be evaluated once, while this has
to be repeated in each SCF iteration if Ṽ(r) changes with the
orbitals. As will be demonstrated in the next section, this
property virtually eliminates the problems with gauge nonin-
variance. Property ~3! ensures size consistency, and property
~4! will be useful for the calculation of a gradient, where
derivatives of Ṽ(r) and v (r) have to be calculated.
Since the exchange-correlation potential is not linear in
the electron density, a superposition of atomic model poten-
tials cannot be used. This can also be drawn from the fol-
lowing consideration: if Ṽ(r) is derived from atomic poten-
tials with the correct ~long-range! 21/r behavior, then a
superposition of such potentials does not have property ~3!.
Even the most approximate density functionals we are using
today generate exchange-correlation potentials which fall off
like r 1/3, which is much slower than the Coulomb potential
 394 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998 Christoph van Wüllen

of a neutral atom. Therefore, it has been decided to use a

superposition of atomic densities ~instead of atomic poten- K U U L EH
^ B m u T̂ ZORAu B n & 5 B m 2
1
2
D Bn 1 B m* ~ r! sp

J
tials! and to derive Ṽ(r) from the electronic Coulomb and
exchange-correlation potentials of the resulting model den- Ṽ ~ r!
3 spB n ~ r ! dr. ~13!
sity. In this way, the exchange-correlation model potential of 4c 22Ṽ ~ r!
2

an atom does not enter other atoms.

In general, exchange-correlation potentials are spin-
dependent. However, it is easier to use a spin-independent
potential to construct v (r) and T̂ ZORA . Furthermore, it has
been decided to use the same model potential irrespective of
the actual density functional used in the calculation. The ac-
tual recipe to calculate v (r) is thus as follows:
• For each atom A, define a spherical model density
r A (r). This density should integrate to a number of
electrons equal to the nuclear charge Z A . To get a
smooth analytical expression for r A (r), it is expressed
as a sum of Gaussian s-functions
This decomposition makes sense if the nonrelativistic kinetic
energy matrix elements can be evaluated analytically. For the
relativistic correction, one must use numerical quadrature.
The modification of the ZORA method presented so far
applies both to the scalar-relativistic one-component scheme
and to the two-component version in which spin-orbit effects
are taken care of.3 Since a two-component density functional
program is currently not available to me, I will further con-
centrate on the scalar-relativistic variant. In this case, the
kinetic energy matrix elements simplify to
^ B m u T̂ SR2ZORAu B n & 5 B m 2 K U U L EH 1
2
D Bn 1 ~ “B m* ~ r !!

rA~r!5p23/2

with the restriction

(i c iA a 3/2
iA exp~2aiAr !,
2
~7!
• ~ “B n ~ r !!
Ṽ ~ r !
4c 22Ṽ ~ r !
2 J dr.

(i ciA5ZA .
• Construct a molecular model density as the sum of the
atomic model densities
r̃~r! 5 (A r̃ A~ u r2RAu ! ,
where the sum is over all atoms in the molecule and RA
the position of atom A.
• Evaluate the electronic Coulomb and exchange correla-
tion potentials of the model density. The Coulomb po-
tential is easily evaluated by means of the incomplete
gamma function F 0 , and for the exchange-correlation
potential, take the spin-unpolarized local density
approximation10
~14!
~8!
Implementing the modified ZORA method in an existing
density functional program is now as simple as adding the
relativistic corrections to the kinetic energy matrix elements
@last term of Eq. ~14!# to the one-electron matrix elements
before the iterative procedure starts. However, the numerical
~9! accuracy of the quadrature is an issue and will be discussed
in the next section. The formulation of an analytical geom-
etry gradient is now a straightforward task. Since one fulfills
the same stationarity conditions as in the nonrelativistic case,
the geometry gradient can essentially be evaluated using the
nonrelativistic code, provided one uses molecular orbitals
and orbital eigenvalues from a ZORA calculation. There is
only one additional contribution to the gradient ~from the
relativistic correction to the kinetic energy matrix elements!
which reads

E EH J
r̃ ~ t ! ] Ṽ ~ r !
ṼC~r ! 5
u r2 t u
dt (
m,n
D mn
]l
~ “B m* ~ r !! •(“B n ~ r ! )
4c 22Ṽ ~ r !
2
dr,
~15!
2
c iA Aa iA F 0 ~ a iA ~ r2RA ! ! ,
Ap (
5 2
~10! with the density matrix D m n and where l is the geometrical
i,A
parameter in question. Since the integral in Eq. ~15! is evalu-
d F LDA~ r̃ ~ r !! ated using numerical quadrature, its geometrical derivative
ṼXC~r ! 5 . ~11!
d r̃ ~ r ! has three different contributions: The first one arises because
the integration grid itself changes with the molecular geom-
• Add the nuclear attraction potential to get Ṽ(r) etry, and the second because the basis functions move with
ZA the nuclei. It is well known how to evaluate these first two
Ṽ~r ! 52
A
(
u r2RA u
1Ṽ C ~ r ! 1Ṽ XC ~ r ! . ~12! contributions as such terms already occur in the nonrelativ-
istic DFT gradient. The third contribution arises since the
model density and thus Ṽ(r) depends on the nuclear posi-
• Now use Ṽ(r) to construct T̂ ZORA via Eq. ~2!. tions. With
The matrix elements of T̂ ZORA between two basis functions
B m and B n can be decomposed into a nonrelativistic part and ] Ṽ ~ r ! 4c 2 ]
5 Ṽ ~ r ! ~16!
a relativistic correction ] l 4c 22Ṽ ~ r !
2
~ 4c 22Ṽ ~ r !! ] l
2 2

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 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998
the problem reduces to the determination of the geometrical
derivatives of Ṽ(r). Let l be the x-coordinate of atom A,x A .
Then the geometrical derivative of the nuclear attraction po-
tential V N (r) is
] x2x A
V N ~ r ! 52Z A . ~17!
]xA u r2RA u 3
Likewise,
] 4
]xA
Ṽ C ~ r ! 5
Ap
~ x2x A ! (i c iA a 3/2
iA F 1 ~ a iA ~ r2RA ! !
and
] d 2 F LDA ~ r̃ ! ]
Ṽ XC ~ r ! 5 r̃ ~ r ! .
]xA d r̃ 2 ]xA
For the geometrical derivative of the model density, one ob-
tains
] F, and Cl, triple-zeta type basis sets from Ref. 12 ~but with
]xA
r̃ ~ r! 52 p 23/2~ x2x A ! (i c iA a 5/2
ia
3exp~ 2 a iA ~ r2RA ! 2 ! .
Thus all quantities necessary to evaluate Eq. ~15! are readily
available.
During the course of this work, van Lenthe and co-
workers published a paper7 in which they also discussed the
use of approximate potentials in the ZORA kinetic energy
operator T̂ ZORA . If we compare both approaches, we see that
Ref. 7 is mainly concerned with reducing the computational
effort, while the present work has analytical geometry de-
rivatives in mind. Reference 7 starts from a sum of atomic
potentials. As explained above, this is only possible if one
disregards the exchange-correlation potential altogether
when constructing T̂ ZORA . Then even further approximations
are made which amount in individually gauging the matrix
elements of T̂ ZORA ~using different potentials for different
matrix elements!.
III. BASIS SETS AND INTEGRATION GRIDS
In first-order relativistic perturbation theory, only non-
relativistic wave functions enter the energy expression and
thus nonrelativistic basis sets can be used. This is not the
case in ZORA calculations. For hydrogenlike systems, one
knows the exact solutions of the ZORA equation,6 and these
are very similar to the large component of the solution of
Dirac’s equation. In molecular ZORA calculations, one thus
expects that the exact orbitals have weak (ln r) singularities
at the nuclear positions. If one uses a finite basis set of, say,
Gaussian basis functions as is done in the present work, one
can never have orbitals with singularities. To get a decent
approximation, one probably needs steeper basis functions as
in the nonrelativistic case. If one uses a large basis set with
highly contracted s shells, it may be sufficient to generate a
new set of contraction coefficients. This route has been fol-
lowed in the present work.
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Christoph van Wüllen 395
To determine suitable contraction coefficients, atomic
calculations with the uncontracted basis sets have been per-
formed. Spherical symmetry has been enforced. The correc-
tions to the kinetic energy matrix elements @Eq. ~14!# have
been calculated in each Kohn–Sham iteration ~i.e., self-
consistently!, using a potential given by Eqs. ~10!–~12!, but
derived from the actual electron density. A large radial inte-
gration grid ~1000 radial shells! with low angular resolution
has been used in these calculations. It has been checked that
2 numerical quadrature of the nonrelativistic kinetic energy
gives results with an error less than 1 m E h . The MO coeffi-
~18! cients obtained in these calculations have then be used to
contract the basis sets. For the Au atom, a 24s17p15d10f
primitive basis set has been taken from Ref. 11 and aug-
mented by one p-function taking the next exponent from the
~19!
well-tempered series. This basis set has been contracted to
18s13p11d7 f . The same procedure has been performed for
the Ag atom (23s16p13d11 p→17s12p10d) and the Cu
atom (20s13p10d11 p→14s10p7d). For the light atoms H,
contraction coefficients from atomic ZORA calculations!
have been augmented by one set of polarization functions
~20!
~H: h p 50.8; F: h d 51.4; Cl: h d 50.65!.
The radial grids used for the atoms are too large to be
used in molecular calculations. Therefore radial integration
grids have been designed that integrate the kinetic energy to
microhartree accuracy in atomic calculations using the con-
tracted basis sets. These grids follow the scheme of Treutler
and Ahlrichs.13 Generally, more radial points are required to
integrate the kinetic energy than the electron density. For
example, 256 radial shells are used for the Au atom, 224 for
Ag, and 160 for Cu. For the heavy elements, the radial points
additionally have to be shifted somewhat to the nucleus,
which is accomplished by increasing the value of the param-
eter a ~Eq. 19 of Ref. 13!. The choice of the angular grid for
a given radial shell follows the experience gained in the non-
relativistic case. Details on these integration grids are avail-
able on request. In general, the number of grid points is 2–3
times higher than required to accurately integrate the
exchange-correlation energy. This is not a serious problem
since in the calculations performed in this work, the ~analyti-
cal! evaluation of the matrix elements of the Coulomb po-
tential is much more expensive than the numerical integra-
tion. Note further than in the calculations we have in mind,
the numerical integration of the kinetic energy matrix ele-
ments is required only once ~and not in each Kohn–Sham
iteration!.
These grids have been used to repeat the atomic calcu-
lations described above, but with the contracted basis sets.
The self-consistent electron density obtained in these calcu-
lations have then been written out. With a separate program,
this density has been expanded in a set of Gaussian
s-functions to determine the parameters c iA and a iA in Eq.
~7! under the constraint given by Eq. ~8!. The Gaussian ex-
ponents a iA have further been restricted to be larger than 0.1.
The parameters minimize the error of the density in the Cou-
lomb norm
 396 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998
TABLE I. First ionization potential of the gold atom.
Method
a
ZORA„MP…
ZORAb
ZORA~ESA!c
DPT-DFTd
n.r. DFTe
rel. CCf
exptl.g
a
Present work: ZORA calculation with a model potential.
b
Unmodified ZORA.
c
ZORA with electrostatic shift approximation, Ref. 2.
d
First-order relativistic density functional calculation.
e
Nonrelativistic density functional calculation.
f
Relativistic coupled cluster calculation, Ref. 23.
g
Ref. 24.
E ~ r ~ r1 ! 2 r̃ ~ r1 !!
1
r 12
~ r ~ r2 ! 2 r̃ ~ r2 !! dr1 dr2 .
This error is smaller than ;0.1 m E h for all atoms, requiring
up to 30 Gaussians for the Au atom. Note that the computa-
tional effort to calculate the model density is negligible, so
the number of Gaussians necessary to calculate the model
densities is not a performance issue. In the atomic calcula-
tions, the energy difference between using the model density
and the fully self-consistent calculations is smaller than
1 m E h . It is expected that in molecular calculations, the nu-
merical accuracy of the relativistic total energy is compa-
rable to the nonrelativistic case. The ZORA~MP! method has
been implemented on top of a density functional program
described earlier.14 This DFT program has been coded within
the TURBOMOLE package.15,16 To evaluate the exchange-
correlation energy, the local density approximation10 plus a
gradient-correction due to Becke17 and Perdew18 has been
used in all calculations.
For comparison, results of first-order relativistic density
functional calculations are also reported. Here, the relativis-
tic corrections have been calculated by means of direct per-
turbation theory ~DPT! as described in Ref. 19. These calcu-
lations require nonrelativistic basis sets. To facilitate the
comparison with the ZORA results, basis sets as described
above have been used in the DPT calculations as well, but
with contraction coefficients taken from nonrelativistic
atomic density functional calculations.
IV. RESULTS AND DISCUSSION
As a first example, let us discuss the first ionization po-
tential of the gold atom. This is a simple but instructive test
case. Table I shows the results of the present work ~given in
boldface! together with data from other calculations and ex-
periment. As already discussed by van Lenthe and
co-workers,2 the result of the unmodified ZORA procedure
~5.21 eV! is quite off because different effective potentials
arise in the neutral atom and the positive ion which are not
handled correctly by ZORA ~since it is not gauge invariant!.
The present method, ZORA~MP!, uses a model potential
which is the same in both cases and thus circumvents the
problem. The ZORA~MP! value is quite close to the result of
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Christoph van Wüllen
Ref. 2 which uses another modification called electrostatic
shift approximation ~ESA!. Compared to experiment, there is
IP @eV#
still an error of ;0.5 eV. However, one should expect errors
9.72 of such magnitude for ionization potentials calculated with
5.21 density functional methods. These errors are generally larger
9.76
9.15 than those for bond dissociation energies and other chemical
7.59 reactions which conserve the number of electrons.20 The rea-
9.08 sons for this behavior are probably well-known deficiencies
9.22 in the long-range part of the exchange-correlation
potential.21,22 The result of Kaldor and Heß23 ~9.08 eV! is
probably the best computational result available today. Note
that spin-orbit interaction changes little since the gold atom
has a single s electron outside a closed shell. This is also
shown by the tiny difference between four-component and
one-component coupled cluster results in Ref. 23 ~9.10 eV
compared to 9.08 eV!. Recently, the present author has de-
veloped a first-order relativistic scheme based on direct per-
~21!
turbation theory.19 In such calculations, it is usually an inter-
esting question whether taking care of relativistic effects
through the leading order is sufficient or if higher-order rela-
tivistic effects are important as well. Since four-component
fully relativistic results ~with comparable basis sets! are not
available for all compounds of the present study, let us ten-
tatively define the higher-order effects as the difference be-
tween the ZORA and DPT results. In the case of the ioniza-
tion potential of the gold atom, there is a large relativistic
effect ~2.13 eV! reflecting the relativistic stabilization of the
6s orbital. At the first-order relativistic ~DPT! level, only
73% of the relativistic effect ~1.56 eV! is recovered.
Note that in contrast to the ZORA~ESA! method, the
ionization potential in the present work is simply calculated
as the difference in total energy between two independent
calculations on the neutral atom and the positive ion. This
may be regarded as a minor advantage in the case of ioniza-
tion potentials, but it is quite important if molecular binding
energies are considered. If energy differences between two
isomers or conformations of a molecule are not ~even con-
ceptually! defined as total energy differences, then in a strict
sense a potential energy surface does not exist. Keeping this
in mind, let us turn to molecular calculations. Table II shows
molecular constants of the coinage metal hydrides CuH,
AgH, and AuH. There is agreement between the present
ZORA~MP! results, the ZORA~ESA! results of van Lenthe,2
and the relativistic density functional results based on the
Douglas–Kroll–Heß transformation.8 Typical errors com-
pared to experiment are 1 pm for bond lengths, 0.2 eV for
binding energies and 30 cm21 for vibrational frequencies.
For CuH, the error in v e is larger but this is a difficult case.26
The density functional calculations perform better than most
of the ab initio methods, although the latter are more expen-
sive by several orders of magnitude. A comparison with the
first-order relativistic ~DPT DFT! results shows the impor-
tance of higher-order relativistic effects: They are small for
CuH and AgH but become important for AuH, where they
affect the binding energy by ;0.3 eV and the vibrational
frequency by ;130 cm21.
For the homonuclear diatomics Cu2, Ag2, and Au2, the
results can be found in Table III. On the whole, the findings
are the same than for the hydrides. For Ag2 and Au2, the
 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998 Christoph van Wüllen 397

TABLE II. Spectroscopic constants of the coinage metal hydrides. TABLE III. Spectroscopic constants of the homonuclear coinage metal di-
atomics.
Compound CuH AgH AuH
Compound Cu2 Ag2 Au2
r e @pm#
a
ZORA„MP… 145 161 152 r e @pm#
ZORA~ESA!b 145 162 154 ZORA„MP…a 221 256 250
DK-DFT 154h ZORA~ESA!b 221 256 252
DPT DFTc 145 162 156 DK-DFT 258f 252f
ab initio 147,e 143f 159,f 163g 150,f 153i DPT DFTc 222 258 258
exptl.d 146 162 152 ab initio 227e 266,e 263g 256,e 249g
exptl.d 222 253h 247
D e @eV#
ZORA„MP…a 3.03 2.52 3.39 D e @eV#
ZORA~ESA!b 3.03 2.55 3.33 ZORA„MP…a 2.18 1.68 2.30
DK-DFT 3.31h ZORA~ESA!b 2.19 1.71 2.26
DPT DFTc 3.02 2.49 3.01 DK-DFT 1.67f 2.27f
ab initio 2.71f 2.20,f 2.37g 311,f 2.92i DPT DFTc 2.17 1.66 2.13
exptl.d 2.85 2.39 3.36 ab initio 1.73e 1.34,e 0.70g 1.87,e 1.78g
exptl.d 2.09i 1.67 2.31
v e @ cm21#
ZORA„MP… a
2012 1788 2277 v e @ cm21#
ZORA~ESA!b 2010 1810 2290 ZORA„MP…a 274 184 176
DK-DFT 2269h ZORA~ESA!b 272 183 174
DPT DFTc 2010 1774 2141 DK-DFT 185f 177f
ab initio 1952,e 2101f 1873,f 1731g 2496,f 2288i DPT DFTc 271 179 165
exptl.d 1941 1760 2305 ab initio 250e 162,e 163g 172,e 186g
exptl.d 265 192 191
a
Present work.
b a
ZORA electrostatic shift approximation, Ref. 2. Present work.
c b
First-order relativistic density functional calculation. ZORA electrostatic shift approximation, Ref. 2.
d c
Reference 25. First-order relativistic density functional calculation.
e d
Relativistic MRCI, Ref. 26. Reference 25.
f e
Relativistic MP2, Ref. 27. Quasirelativistic MCPF, Ref. 29.
g
First-order relativistic CPF, Ref. 28. f
Relativistic ~Douglas–Kroll! DFT, Ref. 8.
h
Relativistic ~Douglas–Kroll! DFT, Ref. 8. g
Relativistic MP2, Ref. 30.
i h
Relativistic coupled cluster, Ref. 23. References 31, 32.
i
Reference 33.

bond lengths are overestimated by 3 pm compared to experi-

ment. Likewise, the vibrational frequencies are too low. It
might be suspected that dispersion forces ~mainly between
the outermost d 10 shells of the two atoms!, which are not
accounted for at the density functional level, are the origin of
this discrepancy. Higher-order relativistic effects amount to
8 pm for the bond length of Au2, 0.2 eV for its bond energy
and 10 cm21 for its vibrational frequency. For Cu2 and Ag2,
higher-order effects are less important. Results for the het-
eronuclear diatomics of the coinage metals, namely CuAg,
CuAu, and AgAu, are found in Table IV. One expects dis-
persion forces to be sizeable in AgAu and indeed finds a
discrepancy between the ZORA and experimental vibrational
frequency ~no experimental bond length is available for
AgAu!. In the copper atom, the 3d shell is less polarizable
than the 4d and 5d shells in Ag and Au, respectively. There-
fore dispersion forces are less important in CuAg and CuAu,
and the bond lengths and vibrational frequencies obtained in
the density functional calculations show better agreement
with experiment. Higher-order relativistic effects amount to
4 pm for the bond lengths of CuAu and AgAu and ;0.3 eV
for their binding energies.
One of the purposes of the present paper is to show that
the ZORA~MP! variant presented here is able to duplicate
the ZORA~ESA! results. Table I–IV confirm this. The dif-
ferences between the two sets of results are quite small and
can be attributed to the use of different basis sets ~Slater-type
basis sets are used in Ref. 2! and the fact that in the ZO-
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RA~ESA! calculations, the gradient corrections to the density
functional have not been accounted for self-consistently, but
in a ‘‘post-LSDA’’ fashion. Having established the validity
of the ZORA~MP! approach, results for the coinage metal
fluorides and chlorides are presented in Tables V and VI. To
my knowledge, no ZORA~ESA! results are available for
these compounds. The fluorides are highly ionic
(M1F2). 44,45 This might be a problem since density func-
tional methods have, for most functionals currently in use,
certain problems describing small negative ions because of
the incorrect long-range behavior of the exchange-correlation
potential.21,22 However, the data obtained in the present work
compare well with the experimental numbers except for the
vibrational frequency of AgF ~30 cm21 discrepancy!. In
agreement with other calculations, the present results show
that AuF is perfectly stable with respect to dissociation. Af-
ter some earlier speculations,40 the existence of AuF as an
isolated molecule could be shown41 and upper/lower bounds
for its binding energy have been estimated based on thermo-
chemical considerations. However, the question whether
larger quantities of AuF can actually be synthesized seems to
be more involved.39
Results for the chlorides CuCl, AgCl, and AuCl are fi-
nally given in Table VI. Here we can again compare with
relativistic Douglas–Kroll–Heß density functional calcula-
tions by Nasluzov and Rösch42 and find agreement except for
the vibrational frequency of AgCl, a discrepancy for which
 398 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998 Christoph van Wüllen

TABLE IV. Spectroscopic constants of the heteronuclear coinage metal TABLE VI. Spectroscopic constants of the coinage metal chlorides.
diatomics.
Compound CuCl AgCl AuCl
Compound CuAg CuAu AgAu
r e @pm#
r e @pm# ZORA„MP…a 205 231 224
ZORA„MP…a 238 233 253 DPT DFTb 206 231 228
ZORA~ESA!b 238 234 254 DK-DFTc 231 223
DPT DFTc 239 237 257 ab initio 225e
ab initio 246,d 238e 239,d 253e 261,d 254e exptl.d 205 228
exptl. 237f 233h
D e @eV#
D e @eV# ZORA„MP…a 3.70 3.06 2.93
ZORA„MP…a 1.92 2.49 2.15 DPT DFTb 3.69 3.06 2.82
ZORA~ESA!b 1.93 2.45 2.15 DK-DFTc 3.07 2.99
DPT DFTc 1.89 2.17 1.91 ab initio 2.89e
ab initio 1.54,d 1.84e 2.16,d 1.79e 1.87,d 2.30e exptl.d 3.96 3.24 3.5
exptl. 1.76f 2.34h 2.07i 21
v e @ cm #
v e @ cm21# ZORA„MP…a 418 324 353
ZORA„MP…a 227 247 187 DPT DFTb 417 323 334
ZORA~ESA!b 229 245 185 DK-DFTc 289 366
DPT DFTc 225 241 176 ab initio 370e
ab initio 193,d 230e 230,d 250e 173,d 202e exptl.d 415 343 383
exptl. 229f,g 248h,g 196k
a
Present work.
a b
Present work. First-order relativistic density functional calculation.
b c
ZORA electrostatic shift approximation, Ref. 2. Douglas–Kroll relativistic DFT, Ref. 42.
c d
First-order relativistic density functional calculation. Reference 25.
d e
Quasirelativistic MCPF, Ref. 29. Quasirelativistic QCISD~T!, Ref. 43.
e
Quasirelativistic CCSD~T!, Ref. 35.
f
Reference 34.
g
DG 1/2 value.
h
Reference 36.
ciation energy, and 17 cm21 in the vibrational frequency.
i
Reference 25. Higher-order ~scalar! relativistic effects change the bond
k
v e -value estimated in Ref. 37. length of AuCl by about 4 pm and its dissociation energy
only by 0.1 eV. The calculations show that the dissociation
energy of AgCl is smaller by ;0.6 eV than for CuCl, which
there is no explanation. High-level quasi-relativistic ab initio is also found experimentally. Going from AgCl to AuCl, the
results by Schwerdtfeger43 are available for AuCl and com- calculations predict a further decrease of the dissociation en-
pare well with the present ZORA~MP! results, the differ- ergy, while the experimental value for AuCl ~3.5 eV! is
ences being 1 pm in the bond length, 0.04 eV in the disso- larger than for AgCl ~3.24 eV!. The experimental value for
AuCl has already been questioned,42,43 but one must not for-
get that all these calculations are scalar relativistic, i.e., do
TABLE V. Spectroscopic constants of the coinage metal fluorides.
not include spin-orbit interaction. The main effect of spin-
Compound CuF AgF AuF orbit interaction in AuCl will be on the dissociation energy
and will just reflect the spin-orbit splitting in the isolated
r e @pm#
ZORA„MP…a 174 201 195
chlorine atom.3 This will lower the dissociation energy, such
DPT DFTb 174 201 199 that the neglect of spin-orbit interaction cannot be the reason
ab initio 173d 198d 190,d 195e for the discrepancy between theory and experiment. It is
exptl.c 174 198 therefore suggested to reconsider the dissociation energy of
D e @eV# AuCl experimentally.
ZORA„MP…a 4.50 3.68 3.39
DPT DFTb 4.49 3.68 3.34 V. CONCLUSIONS
ab initio 2.87e
exptl.c 4.46 3.67 3.0–3.7f A new variant of the zeroth-order regular relativistic ap-
21
v e @ cm #
proximation ~ZORA! has been presented which essentially
ZORA„MP…a 624 482 526 solves the problems associated with the unmodified ZORA
DPT DFTb 622 480 491 procedure. In contrast to other variants like the electrostatic
ab initio 633d 521d 590,d 525e shift approximation, properties like ionization potentials or
exptl.c 623 513 560g molecular binding energies can be computed as energy dif-
a
Present work. ferences. There is now an easy route to molecular geometry
b
First-order relativistic density functional calculation. gradients. Where available, results have been compared with
c
Reference 25. ZORA calculations using the electrostatic shift approxima-
d
Relativistic MP2, Ref. 38.
e tion and complete agreement has been found. Comparison
Relativistic MR-CI, Ref. 39.
f
Estimated bounds, Ref. 41. with relativistic density functional calculations using the
g
Uncertain, Ref. 40. Douglas–Kroll–Heß approach shows that the ZORA method
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 J. Chem. Phys., Vol. 109, No. 2, 8 July 1998 Christoph van Wüllen 399

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