Ab initio relativistic effective potentials with spinorbit operators. II.

K
through Kr
M. M. Hurley, Luis Fernandez Pacios, P. A. Christiansen, R. B. Ross, and W. C. Ermler

Citation: J. Chem. Phys. 84, 6840 (1986); doi: 10.1063/1.450689

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Ab initio relativistic effective potentials with spin-orbit operators. II.
K through Kr
M. M. Hurley, Luis Fernandez Pacios,a) and P. A. Christiansen
Departmento/Chemistry, Clarkson University, Potsdam, New York 13676
R. 8. Ross and W. C. Ermler
Department o/Chemistry and Chemical Engineering, Stevens Institute o/Technology, Hoboken, New Jersey
07030
(Received 10 February 1986; accepted 13 March 1986)
A refined version of the "shape consistent" effective potential procedure of Christiansen, Lee, and
Pitzer was used to compute averaged relativistic effective potentials (AREP) and spin-orbit
operators for the atoms K through Kr. Particular attention was given to the partitioning of the
core and valence space, and where appropriate more than one set of potentials is provided. These
are tabulated in analytic form. Gaussian basis sets with expansion coefficients for the lowest
energy state of each atom are given. The reliability of the transition metal AREPs was determined
by comparing computed atomic excitation energies with accurate all-electron relativistic values.
In all cases the maximum error was found to be less than 0.1 eV. The reliability of the spin-orbit
operators was also considered.

I. INTRODUCTION L is generally taken to be one greater than the largest I quan-

Averaged relativistic effective potentials (AREP) and
spin-orbit (SO) operators for the atoms Li through Ar have
recently been published. 1 This work employed a refined ver-
sion of the "shape consistent" procedure of Christiansen,
Lee, and Pitzer combined with the two-component spinor
formalism of Lee, Ermler, and Pitzer. 3 Wadt and Hay4 have
also published a series of papers providing relativistic shape
consistent effective potentials for most of the transition and
main group elements starting with the first transition row.
However their potentials were typically generated from
Cowan-Griffin atomic wave functions 5 and therefore pro-
vide no ab initio means for obtaining spin-orbit corrections.
In addition their first transition row potentials were ob-
tained nonrelativistically. Martin and Hay 6 have shown that
relativistic corrections even in the first transition row atomic
excitation energies can be substantial.
In this paper we provide shape consistent AREPs and
tum number among the core electrons. Zv is the atomic
number minus the number of core electrons. X lj is a pseudo-
spinor generated from the large component of a Dirac-Fock
valence spinor and Elj is the corresponding energy. Finally
Wlj is the interaction potential (both Coulomb and ex-
change) between X lj and the other valence pseudospinors.
The pseudospinors are given by the equation
Xlj(r) =tPlj(r) + Flj(r), (3)
where tPlj (r) is the numerically tabulated radial function
from the large component of the Dirac-Fock valence
spinor. 7 F/j (r) is chosen to cancel the radial oscillations in
the core region but goes smoothly to zero in the valence
region.
The REP ofEq. (1 ) is then averaged to form the AREP:
U AREP = U~p(r)
L 1

SO operators for the elements of the first transition row. A +L L [UtREP(r) - UtREP(r)] I/,m)(/,ml,
I=Om= -I
more complete review and discussion of the details is given in (4)
Ref. 1 and will not be repeated here.
where
METHOD U~p(r) = 2/~ 1 [lUr,/~I12(r) + (/+ l)Ur,r:1/2(r)].
Relativistic effective potentials (REP) are generated in (5)
the form
L-I 1+112 j
The SO operator then has the formS
U REP = U~p(r) +L L L [U~EP(r) L
I=Oj=I/-1I21 m=-j H SO
= L AUrEP(r)
/=1
(1)
I /+112
where the U~EP(r) are obtained from the two-component X { 21 + 1 m= ~_1I21/,1 + 1I2,m) (/,1 + 1I2,ml
spinor equation
1+1 1-112 }
[ - 1I2V2 ~v + U~p(r) + Wlj ]Xlj = EljXlj' - U-l L 1/,l-1I2,m)(/,I-1I2,ml
- (2) + m= -1+ 112
(6)
where
aj Present address: Department of Chemistry, University of Compiutense,
Madrid-3. Spain. AUFP(r) = Urf: 112 (r) - Ur:t=.112 (r). (7)

6840 J. Chern. Phys. 84 (12). 15 June 1986 0021-9606/86/126840-14$02.10 © 1986 American Institute of Physics

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 Hurley sf al. : Relativistic effective potentials. II
The AREP and SO operators are then fitted to the usual
Kahn-type Gaussian expansions9
The U ~P potentials are fitted directly. The U REP (I < L)
potentials are first modified by subtracting off the "L " func-
tion
U~p(r) = UtREP(r) - UtREP(r)
and then fitted. The exponents determined in Eq. (8) are
then used to fit the SO operators in the form
Uso(r) = _1_AUREP(r).
I 21 + 1 I
CALCULATIONS
AREP and SO operators in the form of Gaussian expan-
sions were generated for the atoms of the first transition row
using the procedures described in detail in Ref. 1. With the
exception ofK and Ca, two sets of potentials (differing in the
core-valence partitioning) were generated for each element.
For all cases the atomic spinors used to generate the poten-
tials were obtained from single-configuration average-ener-
gy Dirac-Fock wave functions. (A point-charge nucleus
was assumed).
For K and Ca the 3s and 3p electrons were included in
the valence space to allow explicit treatment of core-valence
electron correlation in subsequent calculations. The K and
Ca potentials were generated from + 1 and + 2 ionic con-
figurations, respectively. The 4s electrons were removed to
avoid difficulties due to the presence of two valence shells of
the same symmetry. The d spinors for these atoms were ob-
tained by promoting a 3p electron into the 3d shell.
Two sets of potentials were generated for Sc through Zn,
one set using a Ne-Iike core and the other using an Ar-Iike
core. The Ne core potentials were generated from either + 1
(Sc, Cr, Ni, and Cu) or + 2 (Ti, V, Mn, to Co) ionic wave
functions with the 4s electrons again removed. The Ar core
potentials were generated from neutral atomic configura-
tions. 4p spinors were obtained by promoting 3d electrons
into the 4p subshell. In both the Ne and Ar core cases the
open d shell occupations were chosen to remain as close as
possibletoads/ 2 to d 3 / 2 ratio of3 to 2. The Ne core transition
metal potentials, along with the K and Ca potentials, are
given in Table I. The Ar core transition metal potentials are
given in Table II.
Two sets of potentials were also generated for Ga
throughKr. For one (Arcore) the 3d as well as the 4s and 4p
subshells were included in the valence space. These were
generated from neutral atomic wave functions with the
P3/2:Pl/2 ratio kept as close to 2: 1 as possible. The second set
of potentials was generated in a similar manner but included
only the 4s and 4p electrons in the valence shell. d spinors
were obtained by promoting a single electron from the 4p
subshell. The two sets of Ga through Kr potentials are given
in Tables III and IV.
Basis sets for the N e core potentials (K through Zn) are
given in Table V. For K and Ca the exponents were taken
from Wachters 10 (five most diffuse s and four most diffuse p )
J. Chern. Phys., Vol. 84, No. 12, 15 June 1986
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6841
and then reoptimized. For Sc through Zn the Wachters ex-
ponents (7 most diffuse s, 6 most diffuse p, and 5 d) with an
additional diffuse d function from Hayll were used directly
(8) with only the coefficients reoptimized. Basis sets for the Ar
core transition metal potentials are given in Table VI. As in
t the case of K and Ca the exponents were taken from
Wachters and reoptimized. Note that in both Tables V and
VI the p functions for the 4p subshell have been left out. In
(9) molecular calculations these can be taken directly from the
Wachters tables.
Basis sets for Ga through Kr are given in Table VII for
both types of potentials. The exponents were taken from Ref.
4 and reoptimized using the Ar core potentials.
(10)
DISCUSSION
In the past, the reliability of effective potential proce-
dures has been a major issue. However, a large body of evi-
dence (see Ref. 1) demonstrates that, when properly ap-
plied, the shape consistent REP formalism is capable of
reproducing comparable all-electron results to a high degree
of accuracy.
At the present time the most troublesome aspect of ef-
fective potential work involves the partitioning of core and
valence space. It is well known for instance that in the alkali
metals core-valence correlation effects are large enough that
simple one-electron valence space treatments are often en-
tirely inadequate. Similar problems, related to the inclusion
of the 3s and 3p subshells in the valence space, though of
somewhat smaller magnitude, have been observed for the
first transition row metals. 12 The reliability of the Ne core
transition metal potentials (the 3s and 3p electrons are in the
valence space) can be seen in Table VIII where we have
computed atomic excitation energies and compared them
with the essentially exact all-electron values (relativistic and
nonrelativistic) from Ref. 6 and with experimental values
from Moore. 13 When compared to the relativistic all-elec-
tron values the maximum error seen in the effective potential
results is less than 0.1 eV. On the other hand a comparison of
the all-electron relativistic and nonrelativistic values shows
errors of approximately 0.1 to 0.5 eV if relativity is ignored.
That is the errors due to the effective potential approxima-
tion (frozen core, local potential, etc.) are considerably
smaller than the errors in the usual all-electron calculations
which neglect relativity. It has been shown 12 that freezing
the 3s and 3p subshells in the core increases the rd" to
sId" + 1 and d" + 2 excitation energies by about 0.1 and 0.5
eV, respectively. Clearly although the Ar-core potentials of-
fer considerable computational advantage, a price is paid in
terms of the reliability.
A similar question arises in the case of the main group
elements. Should the 3d subshell be included in the valence
space or in the core? Wadt and Hay4 and others have pointed
out that for some of the heavier elements (Tl in particular)
freezing the d subshell in the core can have a substantial
effect on computed molecular properties. It has been gener-
ally assumed that such effects would be small for the lighter
elements. SCF test calculations for GaH using potentials
that included either the 3s, 3p, 3d, and 4p in the valence
space, the 3d, 4s, and 4p or only the 4s and 4p gave bond
6842 Hurley et al. : Relativistic effective potentials. "

TABLE I. AREP and SO operators for K through Zn. The 3s and 3p sub- TABLE I. (continued)
shells (as well as the 4s and 3d) were included in the valence space.
C C
C C n Expn. (AREP) (SO)
n Expn. (AREP) (SO)
I 11.0543 5.545001 0.102875
Potassium 0 3.2657 4.741368 - 0.007 873
s-d 2 2.4103 33.924997
2 2.7745 - 117.521 909 d 2 8.0205 - 2.921409 0.013074
2 3.3369 108.256549 2 23.7316 - 21.510 721 0.087074
I 2.2217 5.803754 2 76.4207 - 53.503053 0.375663
0 12.1945 3.210 232 1 255.1518 - 8.132994 0.602879

p-d 2 3.1546 - 69.975 707 -0.422626

Vanadium
2 4.0319 178.152610 1.728089
s-d 2 2.2253 -46.461235
2 5.1672 - 136.119466 - 1.536318 2 2.7833 98.908827
1 11.3336 4.432282 0.026156
2 3.8053 - 175.341 506
0 1.7433 4.748359 - 0.002 949
2 5.0700 152.276135
1 1.6732 9.725781
d 2 4.9989 - 1.963568 - 0.025 066
0 18.8276 3.107725
2 14.5822 - 15.530 316 0.044 370
2 44.8956 - 38.576 697 0.045586
p-d 2 2.2122 - 17.858910 - 0.183 021
1 141.4835 -7.301014 0.236567
2 2.6253 58.309 347 0.672 799
2 3.5276 - 111.785 050 - 1.554054
Calcium
2 4.7794 115.283333 1.910292
s-d 2 2.6833 29.857190
I 8.1839 - 5.636 391 - 0.400303
2 3.0830 - 117.437361
0 17.3870 5.509440 0.026765
2 3.7066 102.656416
1 2.4765 10.565734
d 2 8.9625 - 3.136448 0.014099
0 13.2889 3.146514
2 26.8093 - 23.110026 0.089784
2 86.5499 - 57.052 871 0.375741
p-d 2 3.4743 - 77.170 204 - 1.192522 1 287.7283 - 8.138 614 0.568594
2 4.3820 180.641728 2.904333
2 5.6621 - 125.808839 - 2.223 356
I 2.2001 5.880944 0.088308 Chromium
0 6.1217 4.769486 -0.006740 s-d 2 3.0836 - 28.406078
2 3.5777 91.176 165
d 2 5.9214 - 2.267 293 - 0,028548 2 4.6527 - 171.883 828
2 17.2037 - 17.175466 0.070031 2 6.1510 181.425 115
2 53.3704 - 42.609 166 0.056660 I 23.5024 10.198945
1 169.9849 - 7.467 668 0.300747 0 20.1691 3.059802

Scandium p-d 2 2.4400 - 18.258059 - 0.214 785

s-d 2 2.1647 - 26.879 376 2 2.8922 59.418 142 0.773559
2 2.5199 86.152006 2 3.8830 - 113.841 801 - 1.743 125
2 3.2800 - 158.358686 2 5.2554 117.491030 2.100 505
2 4.3046 153.652503 1 8.9353 - 4.185364 -0.394159
I 6.1716 - 0.100 351 0 18.8398 5.408047 0.024627
0 15.9083 3.418622
d 2 10.0191 - 3.359 513 0.019023
p-d 2 3.2272 36.969 154 0.584096 2 29.9265 - 24.589 570 0.108092
2 3.8278 - 117.414925 - 1.865295 2 97.3904 - 61.441873 0.499853
2 5.2205 213.542908 3.591338 I 329.0512 - 8.379 354 0.676580
2 7.1372 - 163.694562 2.819652
I 12.8159 5.762162 0.101401
0 4.6662 4.669928 - 0.008 362 Manganese
s-d 2 3.3971 - 28.530 822
d 2 6.9309 - 2.569158 0.007582 2 3.9437 91.919895
2 20.4794 - 19.512482 0.052639 2 5.1351 - 174.687430
2 64.6834 -47.747105 0.198 130 2 6.8187 189.561673
1 208.6899 -7.688084 0.377625 1 24.9023 12.274520
0 21.4236 3.104 753
Titanium
s-d 2 2.0967 - 51.371 918 p-d 2 2.6944 - 18.952995 - 0.227 495
2 2.5442 113.327499 2 3.1889 61.783897 0.833129
2 3.4257 - 173.038673 2 4.2640 - 117.404004 - 1.896890
2 4.6215 146.566730 2 5.7615 120.173337 2.298376
1 1.5006 6.997751 1 9.8544 - 2.765 345 -0.404064
0 18.8498 3.132276 0 20.3261 5.319457 0.023882

p-d 2 3.5379 32.565 195 0.631757 d 2 11.2706 - 3.689 540 0.025722

2 4.2280 - 122.773047 - 2.101364 2 33.6940 - 26.479027 0.132540
2 5.7426 217.986902 4.157391 2 110.9002 - 66.812 691 0.676241
2 7.7763 - 168.728819 - 3.249 611 1 381.8020 - 8.682521 0.815 185

J. Chern. Phys., Vol. 84, No. 12, 15 June 1986

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 Hurley et al. : Relativistic effective potentials. II 6843

TABLE I. (continued). TABLE I. (continued).

C C C C
n Expn. (AREP) (SO) n Expn. (AREP) (SO)

Iron 2 4.4538 63.056955 1.122694

s-d 2 3.4403 - 29.522119 2 6.1763 - 127.180700 - 2.727179
2 4.0606 94.514355 2 8.8393 158.412136 4.087453
2 5.4646 - 185.513 013 1 14.6703 - 5.661282 -0.741858
213.257168 0 30.4335 5.398826 0.036957
2 7.5333
1 4.6628 1.000 943
0 28.7403 3.351345 d 2 16.3016 - 4.732 275 0.063509
2 49.9876 - 34.063 556 0.272004
p-d 2.9446 - 19.132892 2 173.0297 - 90.692 245 1.908336
2 - 0.209 596
1 651.1056 - 10.264 608 1.591 675
2 3.4834 62.185548 0.813 738
2 4.6618 - 118.630095 - 2.016082
2 6.3006 122.397478 2.622968 Zinc
1 10.5654 -1.599610 -0.458125
s-d 2 3.0097 - 25.240201
0 21.8439 - 5.251 981 0.Q25790 2 5.6031 76.248036
2 6.8654 - 184.659460
12.4224 2 10.4260 185.511 071
d 2 - 3.922 736 0.032419
2 37.3163 - 28.149 562 0.161 523 1 2.5611 14.916030
2 124.0691 0 36.7005 3.067735
- 71.936 677 0.874003
1 435.1937 - 8.993 194 0.963903
p-d 2 4.1156 - 28.084925 - 0.301700
Cobalt 2 4.9045 99.617544 1.365287
s-d 2 6.2523 - 140.069070 - 1.100645
2 3.7444 - 30.768 716
96.047186 2 9.4725 151.882706 5.301 359
2 4.4028
5.9451 1 5.8642 - 3.594 321 - 1.063006
2 - 186.837706
2 8.1877 214.131606 0 34.2742 5.292852 0.046324
1 7.6389 3.174801
0 29.8379 3.309296
d 2 17.7045 - 4.952 854 0.076385
2 54.3766 - 35.814241 0.318704
2 190.2643 - 97.186197 2.378813
p-d 2 2.9155 - 28.574965 2.482092
1 733.5532 - 10.759991 1.849286
2 3.6441 90.328092 - 5.318134
2 4.8597 - 157.747831 5.064028
2 6.5213 137.599886 - 1.277768
1 1.7074 1.216568 - 0.182 253
0 24.1178 5.099225 - 0.002 678

d 2 13.7371 -4.218050 0.041777

TABLE II. AREP and SO operators for Sc through Zn. The 4s and 3d shells
2 41.3436 - 30.009900 0.191001
only were included in the valence space.
2 139.1005 -77.760901 1.151240
1 499.1377 - 9.372 248 1.143717
C C
Nickel n Expn. (AREP) (SO)
s-d 2 3.3950 - 48.543110
2 4.3453 106.501 105 Scandium
2 6.1502 - 202.672 719 s-d 2 0.1849 0.030747
2 8.6773 218.644 477 2 1.0102 98.841 829
1 2.4875 7.880363 2 1.1722 - 176.844 282
0 31.8744 3.171606 2 1.4062 99.042517
1 4.1056 8.554347
p-d 2 4.0426 54.267602 3.634658 0 5.1913 3.603574
2 1.7805 1.342317 0.221663
2 5.5321 - 121.264 700 - 4.681761 p-d 2 0.7440 52.921 837 -0.082943
2 7.9169 154.697624 4.987844 2 0.9352 - 114.069565 0.413 865
1 2.2244 - 6.764236 -0.795442 2 1.2587 111.667653 - 1.254232
30.3227 5.445407 0.027092 2 1.6388 - 52.406 766 0.993550
0
1 2.0040 5.548338 - 0.230074
- 4.438070 0.050171 0 1.0705 5.542309 0.017151
d 2 14.8828
2 45.5220 - 32.098 072 0.233592
155.5959 - 84.096072 1.484437 d 2 0.2984 -0.276319 -0.000760
2
571.4202 - 9.794457 1.353811 2 0.9736 - 2.715 285 0.001677
1
2 3.0023 - 10.296417 0.003460
2 12.3967 - 36.817 741 0.001661
Copper 1 47.4688 -13.807665 0.086766
s-d 2 3.7087 - 87.139 577
2 4.5128 209.051201 Titanium
2 5.5338 - 202.305 237 s-d 2 0.2148 0.034806
2 10.2006 154.841898 2 0.9934 21.712488
1 2.6606 9.217435 2 1.1778 - 39.980286
0 32.1793 3.188381 2 1.8148 1.935831
1 0.9321 24.444116
p-d 2 3.6950 -19.075190 -0.302301 0 10.5508 3.186232

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6844 Hurley ef al. : Relativistic effective potentials. "

TABLE II. (continued). TABLE II. (continued).

C C C C
n Expn. (AREP) (SO) n Expn. (AREP) (SO)

p-d 2 0.7632 21.598297 0.325 135 d 2 0.4519 - 0.322372 - 0.002 628

2 1.0675 -72.594682 - 0.868 820 2 1.3863 - 2.421 311 0.008204
2 1.4094 79.001055 0.802186 2 3.7493 - 9.073 354 - 0.004488
2 1.8173 - 38.155 255 - 0.204 820 2 11.5751 - 23.510 959 0.007770
1 0.7956 7.751765 - 0.112 441 1 33.6437 - 11.558001 0.066870
0 0.5835 5.455998 0.003737
Iron
d 2 0.3379 - 0.300060 - 0.001428 s-d 2 0.8173 53.326512
2 1.1144 - 2.861760 0.004476 2 0.9153 - 144.993484
2 3.4282 - 10.930517 - 0.001097 2 1.1071 193.693 196
2 13.6097 - 36.186 640 0.010 587 2 1.3167 - 101.954778
1 45.6994 - 12.745089 0.084493 1 2.0858 20.214622
0 8.9124 3.224127
Vanadium
s-d 2 0.2412 0.046276 p-d 2 0.2229 0.023527 0.000 834
2 1.3137 116.585625 2 1.2954 92.195760 2.290941
2 1.5510 - 206.265 710 2 1.5576 - 187.783854 - 4.922 464
2 1.8956 116.925031 2 1.8904 121.008554 2.761572
1 7.1480 17.728772 1 4.9175 12.368421 -0.069559
0 20.9884 2.970518 0 7.7889 5.203414 0.010 862

p-d 2 0.2058 0.023834 0.000 534 d 2 0.4952 - 0.335382 - 0.003 449

2 0.9444 85.664 988 1.614404 2 1.5039 - 2.398 790 0.011266
2 1.1029 - 168.829453 - 3.288 198 2 3.9669 - 8.887219 - 0.009194
2 1.3138 101.257 101 1.726427 2 11.9067 - 23.245 460 0.016920
1 3.7584 6.586527 - 0.063 205 1 34.9552 - 11.525059 0.070337
0 3.9138 5.590046 0.008963
Cobalt
d 2 0.3773 - 0.316 358 - 0.002 359 s-d 2 0.8670 41.987351
2 1.2352 - 2.866274 0.008 189
2 0.9870 - 118.175362
2 3.7064 - 10.883734 - 0.007 325 2 1.2226 165.507252
2 13.4450 - 30.683 535 0.D15336
2 1.4857 - 86.301432
1 37.7988 - 11.546 134 0.070118
1 2.0696 6.806845
0 1.4786 3.706467
Chromium
s-d 2 0.6040 20.500 301
p-d 2 0.2469 0.026888 - 0.000 580
2 0.7093 - 65.953 875
2 1.4054 97.555221 2.463348
2 0.9042 115.603408
2 1.6675 - 178.493 098 - 4.815158
2 1.0918 - 68.626 681
2 2.0793 108.753857 2.318868
1 1.7395 13.323779
1 5.2615 12.923869 - 0.214 587
0 8.3722 3.152809
0 8.0935 5.227323 0.012912
p-d 2 0.1756 0.019634 -0.000 122
d 2 0.5323 -0.328277 - 0.003101
2 1.0206 96.546965 1.952357
2 1.5365 - 2.079 793 0.008766
2 1.1934 - 186.337208 - 3.897 724
2 3.8742 - 7.911 246 -0.003064
2 1.4436 109.437382 1.941 335
2 10.9693 - 20.625 631 0.006849
1 4.1637 7.510 340 - 0.123 406
1 32.2444 - 11.212 105 0.067773
0 4.5690 5.510 864 0.011417

d 2 0.3374 - 0.189848 - 0.001457 Nickel

2 1.1044 - 2.217 074 0.003171 s-d 2 0.9379 43.799377
2 3.4444 - 10.171 613 0.004179 2 1.0665 - 122.488278
2 13.0950 - 31.332 519 - 0.002 219 2 1.3201 170.382907
I 41.7010 - 12.178556 0.084857 2 1.6045 - 88.123 616
1 2.2698 8.001575
Manganese 0 1.7094 3.674683
s-d 2 0.7461 50.562812
2 0.8365 - 139.925717 p-d 2 0.2653 0.027447 0.000384
2 1.0087 187.175203 2 1.5092 94.021 553 2.678064
2 1.1953 - 96.709 875 2 1.8128 - 187.115489 - 5.647 966
1 1.9589 18.296155 2 2.2120 122.751965 3.072 273
0 8.9204 3.136734 1 5.4856 12.053374 - 0.138428
0 7.5189 5.363713 0.012259
p-d 2 1.0937 35.466611 0.906615
2 1.4857 - 103.008 045 - 2.527192 d 2 0.6047 -0.398208 - 0.003 842
2 1.9708 106.408 115 2.414645 2 1.9370 - 3.115 495 0.012924
2 2.5991 - 43.289 204 - 0.831584 2 5.4946 - 11.885995 -0.005573
1 1.0445 10.657283 - 0.064 970 2 18.0895 - 32.509 995 0.021615
0 3.0091 5.335990 - 0.000 109 1 53.1894 - 11.935028 0.122379

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 Hurley et al. : Relativistic effective potentials. II 6845

TABLE II. (continued). TABLE III. (continued).

C C C C
n Expn. (AREP) (SO) n Expn. (AREP) (SO)

Copper Germanium
s-d 2 0.8115 6.229032 s-d 2 2.3051 - 27.651406
2 1.1074 -48.317299 2 2.6710 157.555352
2 1.3803 113.068708 2 3.4944 - 208.908 895
2 1.6538 - 65.061849 2 4.6654 146.752999
I 2.9094 19.981919 1 14.9254 26.790658
0 10.4748 3.217010 0 44.0453 2.946861

p-d 2 0.7347 35.695530 0.542054 p-d 2 1.7214 - 55.524955 - 2.085 862

2 0.8359 - 103.460 066 - 1.910 771 2 1.9893 194.353084 7.286614
2 1.0323 151.972 303 3.657981 2 2.5563 - 249.205 886 - 9.799 538
2 1.2530 - 87.702 876 - 2.591184 2 3.2926 154.476650 4.558531
I 2.3218 20.809 243 O.ot8 191 I 8.2693 13.029046 - 0.300639
0 9.2042 4.792951 -0.021531 0 10.1499 5.374356 0.013 868

d 2 0.4751 -0.172871 - 0.002171 d 2 1.3546 - 1.401 967 - 0.026 718

2 1.4237 - 1.670338 0.003162 2 5.0223 - 9.454036 0.150711
2 4.0396 - 8.224877 0.009 606 2 15.3283 - 23.624096 -0.344443
2 12.4439 - 23.395144 -0.004260 2 47.4731 - 62.446 718 0.892186
I 38.7404 - 11.426 145 0.090928 I 136.2421 -12.963660 0.291613

Zinc Arsenic
s-d 2 1.1319 54.526363 s-d 2 1.6098 34.113517
2 1.2847 - 151.996 139 2 1.8180 - 190.881484
2 1.5899 214.513 097 2 2.2564 198.610934
2 1.9354 - 113.678441 2 2.8134 - 128.755823
I 3.1665 20.791293 I 3.8534 32.516864
0 15.2570 3.026611 0 16.4907 3.337814

p-d 2 0.8456 37.360401 0.861562 p-d 2 1.9270 - 68.503383 - 2.274 314

2 0.9624 - 108.311 316 - 2.861396 2 2.2560 231.131508 7.983322
2 1.1985 166.686203 5.266790 2 2.9673 - 286.992 524 - 10.698943
2 1.4630 - 102.955786 - 3.730736 2 3.9398 179.058949 4.812324
I 2.1912 9.700778 0.111 511 I 11.1320 12.129965 - 0.363 536
0 1.6172 5.595258 -0.030553 0 11.2240 5.372 975 0.016596

d 2 0.7062 -0.425633 - 0.004 310 d 2 1.7411 - 2.034656 -0.011 108

2 2.2700 - 3.323 037 0.014017 2 6.7374 - 13.089098 0.079210
2 6.4779 -12.901469 - 0.000 166 2 21.8949 - 30.309 260 -0.093110
2 21.3700 - 35.579 939 0.021247 2 63.2840 -73.837470 0.473842
I 63.2556 - 12.051 876 0.158499 I 186.7813 -13.682019 0.508968

Selenium
s-d 2 2.5856 -76.463899
TABLE III. AREP and SO operators for Ga through Kr. The 4s, 4p, and 3d 2 3.0434 269.160 486
subshells were included in the valence space. 2 4.0329 - 307.330938
2 5.3989 196.385623
C C I 18.1870 29.189408
n Expn. (AREP) (SO) 0 55.4028 2.910 986

Gallium p-d 2 2.1683 -72.785184 - 2.764486

s-d 2 1.2979 47.459923 2 2.5785 252.061761 10.056624
2 1.4656 - 133.318512 2 3.4859 - 313.299148 - 14.089499
2 1.8081 198.618 181 2 4.7979 200.910 715 6.427227
2 2.2098 - 111.652 731 1 14.7490 12.055689 - 0.523 227
I 3.4107 26.529903 0 13.4645 5.316860 0.024649
0 13.7580 3.208416
d 2 2.1182 - 2.586 387 -0.058154
p-d 2 1.6081 - 22.179 537 - 1.015863 2 8.2432 - 15.599658 0.338325
2 1.8308 116.834628 4.595739 2 28.6778 - 41.256 958 -0.858819
2 2.3145 - 173.272 676 - 7.005 394 2 93.8581 - 98.637 849 2.725459
2 2.9641 116.797787 3.473356 1 239.6398 - 12.614325 0.515995
1 6.9474 13.537562 - 0.249163
0 9.3454 5.370638 0.012874 Bromine
s-d 2 1.8138 41.542666
d 2 0.9736 - 0.774 710 -0.036522 2 2.0770 - 130.865 307
2 3.2530 -5.183851 0.181918 2 2.6514 229.111 352
2 9.1203 - 16.362835 -0.412378 2 3.3914 - 139.158807
2 30.2036 - 46.293 059 0.944826 1 5.0794 34.691664
I 87.7854 - 12.367616 0.104 359 0 22.0086 3.138916

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6846 Hurley et al. : Relativistic effective potentials. II

TABLE III. (continued). TABLE IV. (continued).

C C C C
n Expn. (AREP) (SO) n Expn. (AREP) (SO)

Germanium
p-d 2 2.3438 - 68.312085 - 2.114400 2 1.8836 - 37.252099
s-J
2 2.7900 236.411 370 8.375434 2 2.3351 118.111 483
2 3.7750 - 285.209 689 - 12.007087 2 3.1864 - 155.077 091
2 5.2240 192.274858 5.418710 2 4.2719 84.980302
1 15.2242 13.296482 - 0.570016 1 2.0359 19.088362
0 14.2093 5.337790 0.023705 0 12.9292 3.267818
d 2 2.5478 - 3.207 467 - 0.039 374 2 1.6450 - 53.611416
P-J - 1.322626
2 9.9043 - 17.819559 0.262533 2 1.9419 175.172 210 5.108507
2 32.9439 - 41.367 750 - 0.562529 2 2.5600 - 215.375 755 - 7.282 195
2 98.6328 - 102.009 529 2.001467 2 3.3872 139.209299 3.449724
1 287.7808 - 13.964 525 0.751481 1 8.4168 10.595574 - 0.248105
0 9.8071 5.457020 0.012796
Krypton
s--d 2 2.9872 -78.361242 2 0.8998 64.171476
d-J - 1.155727
2 3.6064 278.319626 2 1.0345 - 161.126524 3.207308
2 4.9812 - 296.609 320 2 1.2995 186.054430 -4.009919
2 7.0405 197.151 131 2 1.6096 - 92.987 980 2.140861
1 22.7210 - 13.340 942 1 2.2458 10.200619 - 0.122 642
0 21.7127 3.352396 0 1.7226 7.640 654 0.016388
p-d 2 2.6125 -73.707856 - 2.193 868 2 0.7677 - 0.394 331
J - 0.001 193
2 3.1575 262.283 199 8.954964 2 2.0840 - 5.838442 - 0.073 989
2 4.3900 - 317.215 031 - 13.152760 2 5.4301 - 25.135115 0.064705
2 6.3053 218.150173 5.942030 2 16.5329 - 54.325 540 0.100 360
1 19.6323 13.320876 - 0.595870 1 50.3290 - 19.005036 0.199126
0 17.4334 5.268356 0.025365
Arsenic
d 2 3.0551 - 3.989469 -0.012220 2 2.1576 - 49.068825
s-J
2 12.0960 - 21.258 189 0.133 190 2 2.6094 175.889361
2 41.9116 - 50.230622 0.002125 2 3.5238 - 200.331 650
2 122.3773 - 113.973645 1.148264 2 4.8202 150.991764
1 363.4737 - 14.670471 1.091 852 1 13.8706 32.852 165
0 35.6765 3.339107

P--J 2 1.9185 - 67.207 995 - 1.752730

TABLE IV. AREP and SO operators for Ga through Kr. The 4s and 4p 2 2.2670 220.362870 6.673104
subshells only were included in the valence space. 2 3.0129 - 270.246 920 - 9.459 449
2 4.0439 173.095280 4.405351
C C I 11.3364 10.388259 - 0.318555
n Expn. (AREP) (SO) 0 11.3746 5.429486 0.016261

Gallium d-J 2 0.8371 - 38.583497 -0.680830

s-J 2 0.3208 - 0.042 524 2 0.9505 117.567784 0.757369
2 2.6202 127.490679 2 1.1801 - 167.236407 - 1.853 199
2 3.1413 - 239.205 661 2 1.4542 106.399342 0.774252
2 3.9005 113.471856 1 4.5444 9.161246 - 0.014977
1 2.4885 25.328977 0 4.1572 7.609508 0.001340
0 13.4034 3.349783
J 2 0.9589 - 0,473 017 -0.003267
P--J 2 1.3366 - 33.185 229 - 1.055604 2 2.5418 - 6.785 312 - 0.049 499
2 1.5978 112.459403 4.069051 2 6.5134 - 28.133 385 0.079822
2 2.0987 - 136.701481 - 5.946 895 2 20.0331 - 60.481985 0.032690
2 2.6994 82.935359 3.021091 1 60.1870 - 19.244002 0.252627
1 4.3282 11.972 970 - 0.174 668
0 8.2118 5.430342 0.007396 Selenium
s-J 2 2.5309 -77.680224
d-J 2 0.7592 52.299481 0.663090 2 3.0163 259.822746
2 0.8562 - 124.251 961 - 1.430938 2 4.0524 - 286.509 483
2 1.0315 130.492963 1.212184 2 5.4961 186.876955
2 1.2319 - 60.306 935 - 0.455 995 1 15.2147 14.901224
1 1.9223 14.735067 0.007970 0 19.2907 3.385407
0 5.1576 3.488669 - 0.001 172
P--J 2 2.1523 - 72.917127 - 2.723 256
J 2 0.5881 - 0.319 977 0.000 539 2 2.5666 242.852829 10.002583
2 1.6407 - 4.770944 - 0.008 480 2 3.4651 - 298.234 401 - 14.600980
2 4.3550 - 21.727 410 0.041 166 2 4.6665 156.365 132 8.375164
2 13.1166 - 48.097 948 0.008135 1 3.8923 14.579875 - 0.520929
1 40.7440 - 18.713 619 0.155726 0 13.9783 5.288504 0.023710

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 Hurley et al. : Relativistic effective potentials. II 6847

TABLE IV. (continued). TABLE IV. (continued).

C C C C
n Expn. (AREP) (SO) n Expn. (AREP) (SO)

d-f 2 1.0588 - 42.698 303 - 0.506 930 f 2 1.4019 - 0.689 622 -0.004659
2 1.2139 130.758051 1.469425 2 3.6020 - 8.903 298 - 0.102 547
2 1.5417 - 186.894124 - 1.758 140 2 8.9670 - 33.985 401 0.195105
2 1.9503 124.371037 0.819799 2 28.1352 - 74.117 600 -O.oJ8745
I 6.0305 9.393292 -0.029384 1 83.3179 - 19.702532 0.388454
0 5.3690 7.530381 0.002918
Krypton
f 2 1.1650 - 0.560 052 - 0.001224 5-f 2 3.0087 - 81.186060
2 3.0193 -7.654434 -0.012529 2 3.6167 277.684654
2 7.6363 - 30.986436 0.077099 2 4.9391 - 298.012 342
2 23.7388 - 66.839419 - 0.014 666 2 6.6758 143.602269
1 70.7477 - 19.464 551 0.310069 I 5.2485 17.648469
0 22.3951 3.336640
Bromine
5-f 2 1.8460 39.554527 p-f 2 2.6469 -76.909 832 - 2.293804
2 2.1168 - 127.327067 2 3.1865 267.189499 9.377 138
2 2.7039 226.224707 2 4.3992 - 323.519297 - 13.887917
2 3.4514 - 137.277 730 2 6.2587 220.480046 6.452271
1 5.1803 34.878343 1 19.3473 11.694519 - 0.533 479
0 23.0345 3.163496 0 17.3469 5.331181 0.023956

p-f 2 2.3765 -72.414036 - 1.770430 d-f 2 1.5223 - 48.586225 - 0.920 988

2 2.8200 241.876011 7.445 156 2 1.7836 156.378 100 2.706 610
2 3.7950 - 289.872 685 - 10.970508 2 2.3501 - 225.409 555 - 3.363 946
2 5.2060 193.861761 5.093142 2 3.1368 161.852199 1.630381
1 14.6970 11.547855 - 0.435348 1 9.7851 10.137445 - 0.085888
0 14.2892 5.401446 0.019296 0 8.5497 -7.399992 0.006859

d-f 2 1.2216 -42.921552 -0.977 748 f 2 1.6775 -0.867674 -0.006144

2 1.4061 132.842701 2.501792 2 4.2455 - 10.168666 - 0.059 861
2 1.7967 - 190.214086 - 2.647 221 2 10.4133 - 37.047 831 0.171257
2 2.2993 130.493379 1.125519 2 33.0191 - 82.028 862 - 0.025887
1 6.9687 9.658866 - 0.027 344 1 97.5401 - 19.952639 0.463731
0 6.2013 7.503 121 0.002062

TABLE V. Gaussian basis sets for K through Zn generated from AREPs which included the 35 and 3p (as weJI as the 45 and 3d) subshells in the valence space.
Numbers in parenthesis are orbital energies in hartree.

Expn. C (n = 3) C (n = 4) Expn. C (n=3) C (n = 4)

Potassium Calcium
s 2.889 - 0.357 900 0.079654 3.335 - 0.382 758 0.110184
0.8196 0.655080 - 0.157 670 0.9892 0.661085 0.220350
0.3127 0.579747 -0.288046 0.3977 0.587 173 0.346460
0.03388 0.015885 0.738296 0.06394 0.013 693 0.665992
0.01725 -0.007494 0.360 381 0.02670 -0.004178 0.488642

P 8.714 - 0.032 020 10.55 - 0.035 971

1.089 0.355737 1.326 0.310 124
0.590 6 0.430529 0.7696 0.448977
0.2267 0.342939 0.3007 0.339783

Scandium Titanium
( - 2.592 8) (-0.2108) ( - 2.908 3) ( - 0.2217)
s 36.58 -0.013028 0.003247 39.81 -0.010 792 0.002564
11.04 0.067500 - O.oJ5 124 12.22 0.060686 - 0.012 964
4.491 - 0.398686 0.107458 5.009 0.405335 0.107391
1.129 0.619051 -0.204 766 1.286 0.635627 - 0.207195
0.4546 0.603067 -0.351952 0.5128 0.594599 -0.337902
0.07753 0.001667 0.622560 0.08558 0.002044 0.617 599
0.03079 0.001959 0.539432 0.03330 0.001639 0.540009

( 1.575 1) ( - 1.7992)
P 32.59 - 0.008 548 36.37 -0.007583
13.22 - 0.000 755 14.78 -0.004904
5.584 - 0.065397 6.275 -0.067020

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6848 Hurley et al. : Relativistic effective potentials. II

TABLE V. (continued).

Expn. C (n = 3) C (n = 4) Expn. C (n = 3) C(n=4)

2.186 0.239209 2.479 0.251923

0.8950 0.597355 1.016 0.596821
0.3520 0.297954 0.3982 0.288886

( - 0.335 4) ( - 0.4317)
d 22.43 0.020854 25.99 0.022173
6.035 0.110 457 7.086 0.117824
1.979 0.304 105 2.349 0.319831
0.6668 0.457771 0.8002 0.468462
0.2182 0.384376 0.2620 0.358735
0.05880 0.093829 0.07200 0.071 308

Vanadium Chromium
( - 3.2290) ( - 0.2319) ( - 3.5569) ( - 0.2417)
s 43.25 -0.009034 0.002038 46.37 -0.007582 0.001610
13.51 0.055 107 -0.011248 14.82 0.049631 -0.009 594
5.567 -0.409 361 0.106 531 6.133 - 0.412 313 0.105304
1.452 0.645757 - 0.206980 1.630 0.651541 - 0.204 821
0.5744 0.590024 - 0.325 408 0.6412 0.589027 - 0.314 868
0.09282 0.002747 0.618081 0.09551 0.004334 0.621373
0.03553 0.001 181 0.534621 0.3759 0.000 341 0.526145

(- 2.026 5) ( - 2.259 8)
P 40.32 - 0.010 349 43.20 - 0.010112
16.46 0.004689 17.78 0.001231
7.024 - 0.071800 7.661 -0.071922
2.790 0.259188 3.077 0.276245
1.146 0.596145 1.266 0.591470
0.4473 0.283967 0.4935 0.274418

(-0.5004) ( - 0.5588)
d 30.22 0.022431 34.02 0.023088
8.272 0.121 119 9.432 0.124527
2.758 0.327129 3.159 0.333931
0.942 1 0.472 578 1.080 0.474107
0.3053 0.349066 0.3466 0.341 319
0.08200 0.063194 0.09120 0.058317

Manganese Iron
( - 3.888 6) ( - 0.250 3) ( - 4.257 9) ( - 0.2614)
s 49.12 - 0.006123 0.001 196 53.50 - 0.Ql5 485 0.003527
16.09 0.044445 - 0.008 047 17.72 0.072 914 - 0.014 782
6.704 - 0.415 655 0.103816 7.377 - 0.432 651 0.106541
1.805 0.666812 - 0.204 869 2.018 0.665238 - 0.203188
0.7030 0.579621 - 0.302 873 0.7799 0.586413 -0.297126
0.1064 0.004455 0.619505 0.1142 0.004 795 0.627001
0.03962 0.000 129 0.524170 0.041 89 -0.000047 0.513 742

(- 2.4961) ( - 2.763 8)
P 44.61 - 0.010 356 49.12 -0.009 694
18.60 -0.002189 20.50 - 0.005 483
8.138 -0.072472 8.987 - 0.070899
3.337 0.299972 3.682 0.305922
1.379 0.581 571 1.522 0.581 179
0.5386 0.264434 0.5927 0.259143

(- 0.627 3) ( - 0.634 2)
d 37.90 0.023919 41.45 0.024975
10.52 0.129626 11.54 0.135247
3.538 0.341773 3.885 0.348696
1.212 0.474847 1.324 0.471 837
0.3879 0.329452 0.4167 0.324858
0.1054 0.053610 0.113 3 0.054924

Cobalt Nickel
( - 4.631 6) (- 0.2714) ( - 5.0162) ( - 0.280 7)
s 56.12 - 0.013 829 0.003066 59.26 -0.012413 0.002661
18.92 0.066060 - 0.012 870 20.37 0.059874 - 0.011 158
7.952 -0.434564 0.105682 8.594 -0.434274 0.104 079
2.198 0.686171 -0.207637 2.394 0.698362 -0.208601

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 Hurley et al. : Relativistic effective potentials. II 6849

TABLE V. (continued).

Expn. C (n = 3) C(n=4) Expn. C (n = 3) C (n = 4)

0.8467 0.570679 - 0.285 229 0.9182 0.561819 - 0.275718
0.1223 0.005740 0.627618 0.1302 0.006025 0.627224
0.04417 - 0.000610 0.510 981 0.04639 - 0.000 835 0.509020

(- 3.0344) ( - 3.3124)
P 49.24 - 0.010 392 53.17 - 0.014202
20.75 - 0.010 594 22.39 0.003736
9.204 - 0.065 415 9.928 - 0.073329
3.818 0.348852 4.116 0.366242
1.588 0.562280 1.710 0.555590
0.6247 0.235624 0.672 5 0.227109

(-0.6617) (- 0.692 6)
d 44.98 0.026164 48.94 0.027018
12.57 0.140 828 13.72 0.145080
4.244 0.355210 4.640 0.360 225
1.443 0.469364 1.574 0.467673
0.4500 0.318688 0.4864 0.313 989
0.1219 0.054267 0.1316 0.053618

Copper Zinc
( - 5.412 2) (- 0.289 9) ( - 5.814 7) (- 0.298 0)
s 64.63 - 0.010798 0.002237 68.59 - 0.009 346 0.001864
22.14 0.054887 -0.009846 23.71 0.048904 -0.008331
9,347 -0.432320 0,102198 10,04 - 0.430 731 0.100 284
2.609 0,699674 - 0.205 952 2.810 0.712603 - 0.206 986
0.9972 0.561074 - 0.270 595 1.070 0.550260 - 0.260604
0,140 1 0.005981 0.614643 0.1470 0.006124 0.619320
0,04936 - 0.000 816 0.519954 0.051 14 - 0.001017 0,512923

( - 3.5999) (- 3.8913)
P 60.48 -0.012897 66.08 - 0.012 090
25,36 0,000683 27.69 - 0.002552
11.17 - 0.071092 12.18 - 0.069 281
4.564 0.356761 4.988 0.354730
1.884 0.563904 2.058 0.565351
0.7347 0.227141 0.7986 0.227803

( - 0.724 5) (- 0.764 9)
d 53,65 0,027281 58.41 0.027602
15,07 0.147035 16.45 0.149206
5.104 0.362571 5.576 0,354730
1.727 0.467552 1.884 0.468041
0,5283 0.310915 0.572 3 0.303367
0,1491 0.054021 0.1908 0.053632

TABLE VI. Gaussian basis sets for Sc through Zn generated from AREPs which included only the 4s and 3d subshells in the valence space.

Expn. C Expn. C

Scandium Titanium
4s 1.129 0.035430 1.286 0.038135
0.4512 -0.302476 0.5273 - 0,295 658
0.07760 0.611 806 0.08545 0,603586
0,03027 0.543082 0.03290 0,544 140

3d 12.23 0.053111 13,86 0,059376

3,151 0.233677 3.600 0,257029
0.9874 0.425761 1.138 0,442549
0.3482 0.398111 0.413 9 0.377132
0.1256 0,239489 0.1517 0.207119

Vanadium Chromium
4s 1.351 0.043 111 1.629 0,006194
0.600 8 - 0.284946 0.5124 -0,273336
0,09275 0,599744 0.1060 0.605083
0.03482 0.541693 0.03778 0.565932

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6850 Hurley et at. : Relativistic effective potentials. II

TABLE VI. (continued).

Expn. C Expn. C

3d 16.49 0.059210 18.64 0.061991

4.294 0.260308 4.940 0.268574
1.357 0.452098 1.586 0.453499
0.4861 0.374363 0.5810 0.362659
0.1807 0.194581 0.2161 0.190 379

Manganese Iron
4s 1.805 0.027952 1.921 0.016460
0.700 1 - 0.265 969 0.7000 -0.260057
0.1120 0.565 114 0.113 9 0.648 729
0.041 17 0.575 115 0.04042 0.499444

3d 21.54 0.060 527 24.08 0.061396

5.670 0.267731 6.376 0.271 333
1.830 0.441316 2.037 0.449194
0.6874 0.367201 0.7593 0.343495
0.2414 0.204974 0.2913 0.215960

Cobalt Nickel
45 2.017 0.011884 2.362 0.010376
0.7330 -0.247035 0.8079 -0.238384
0.1202 0.667223 0.1275 0.665229
0.041 71 0.480405 0.04398 0.477461

3d 26.64 0.062973 28.73 0.065209

7.071 0.276196 7.726 0.280565
2.251 0.454515 2.496 0.443502
0.8039 0.361 318 0.9166 0.359627
0.2857 0.194932 0.310 5 0.205313

Copper Zinc
45 2.449 0.010280 2.797 0.014108
0.8596 - 0.200289 0.9982 -0.229491
0.1192 0.512944 0.1454 0.655988
0.04177 0.602 319 0.04622 0.484348

3d 31.84 0.062762 34.46 0.066622

8.498 0.273 012 9.325 0.286257
2.684 0.443200 2.976 0.457952
0.9108 0.371371 1.044 0.354736
0.2890 0.231526 0.3666 0.190234

lengths of 3.12, 3.11, and 3.17 bohr, respectively, and vibra-
tional frequencies of 1811,1826, and 1714cm- 1, respective-
ly. All three calculations employed the same (5s, 5p, 2d)
Slater basis for gallium and a (1$, Ip) Slater basis for the
hydrogen. Although freezing the 3s and 3p in the core has
negligible effect (at least at the SCF level) freezing the 3d
appears to have a significant effect on both bond lengths and
vibrational frequencies.
For ease of comparison, the above discussions were
based strictly on AREP results. On the other hand the pri-
mary advantage of the present procedure over that employed
in Ref. 4 is due to presence of an ab initio spin-orbit operator.
A detailed discussion of the reliability of the SO formalism
employed here has been given by Ross et 01. 14 In addition we
have computed SO splittings for several elements and ions of
the first transition row using AREPs, SO operators and basis
sets form the present Tables I, III, V, and VII. These values,
along with all-electron and experimental results, are listed in
Table IX. For the main group elements the errors due to the
use of the effective SO operator are small, whereas for the
transition elements errors are around 10% or even larger. As
elaborated by Ross et 01., the SO operator for the highest L
quantum (the residual potential) exhibits the expected l!r
behavior which leads to somewhat larger errors in fitting the
operators and to difficulties with orbital basis set expansions.
Muller et 01.15 have argued that for calculations involv-
ing lighter elements and extensive electron correlation the
computational advantages of effective potential treatments
dissappear since the time consuming step is typically the
configuration interaction. This would be correct in many

J. Chern. Phys., Vol. 84, No. 12, 15 June 1986

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 Hurley et at : Relativistic effective potentials. II 6851

TABLE VII. Gaussian basis sets for Ga through Kr generated from AREPs which included the 3d subshell either in the core (4s4p) or in the valence
(3d 4s4p). The numbers in parentheses are orbital energies in hartree.

Expn. C (4s4p) C (3d4s4p) Expn. C (4s4p) C (3d4s4p)

Gallium Germanium
( - 0.432 6) ( - 0.424 7) ( - 0.564 3) (- 0.559 2)
4s 0.9738 -0.294946 -0.290252 1.018 - 0.381386 - 0.376 570
0.2215 0.622622 0.597936 0.3188 0.634809 0.616652
0.07653 0.569165 0.590020 0.1030 0.634968 0.648652

(- 0.2060) ( - 0.202 5) (- 0.2849) ( - 0.2821)

4p 1.708 - 0.034 695 - 0.034 363 1.836 -0.046097 -0.045659
0.2018 0.495020 0.474638 0.2622 0.536154 0.523098
0.05750 0.618 130 0.637128 0.07976 0.573414 0.585967

( - 1.1097) ( - 1.5475)
3d 39.56 0.064 707 44.88 0.062545
10.68 0.290611 12.25 0.285448
3.280 0.520701 3.832 0.523108
0.9131 0.430744 1.106 0.423674

Arsenic Selenium
( - 0.699 9) (- 0.695 2) ( - 0.856 7) ( -0.8534)
4s 1.221 - 0.363583 -0.360964 1.340 -0.388566 -0.386743
0.3200 0.735364 0.722469 0.3717 0.788462 0.779391
0.113 8 0.506620 0.517456 0.1322 0.476038 0.483679

( - 0.3675) ( - 0.3653) ( -0.4000) ( - 0.398 4)

4p 1.976 - 0.055 064 -0.054625 2.142 - 0.058 962 -0.058712
0.3232 0.566079 0.557032 0.3854 0.580848 0.574861
0.1024 0.542313 0.551 143 0.1195 0.533513 0.539401

( - 2.019 7) ( - 2.549 8)
3d 50.14 0.061335 55.15 0.060746
13.81 0.282645 15.38 0.280618
4.383 0.525483 4.947 0.528041
1.304 0.415846 1.506 0.408321

Bromine Krypton
( - 1.0165) ( - 1.013 8) (- 1.1843) ( - 1.1825)
4s 1.380 - 0.510695 -0.508319 1.597 -0.440 328 - 0.439 316
0.5223 0.776052 0.768066 0.4865 0.873258 0.868242
0.172 7 0.601393 0.607121 0.1694 0.436970 0.441180

( - 0.453 7) ( - 0.4525) ( -0.5211) ( - 0.5205)

4p 2.537 - 0.065 975 -0.065692 2.666 -0.069352 -0.069626
0.4497 0.595214 0.590 587 0.5176 0.609 999 0.607144
0.1396 0.520679 0.525242 0.1618 0.507905 0.510 881

(-3.1094) ( - 3.705 2)
3d 62.41 0.057949 68.53 0.057099
17.27 0.277 462 19.02 0.276538
5.583 0.530688 6.195 0.533233
1.732 0.404904 1.954 0.398730

J. Chem. Phys .• Vol. 84. No. 12. 15 June 1986

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6852 Hurley at a/. : Relativistic effective potentials. II

TABLE VIII. Computed transition metal excitation energies (in eV) obtained from SCF calculations using
AREPs which included the 3s, 3p, 3d, and 4s subshells in the valence space. All-electron relativistic (HFR) and
nonrelativistic (NHF) values from Ref. 6 as well as experimental values from Ref. 12 have been included for
comparison.

Atomic State AREP HFR NHF Expt

Sc ld l 2D 0.00 0.00 0.00 0.00

Sc s ld 2 4F 1.07 1.12 1.00 1.43
Sc d3 4F 4.62 4.65 4.47 4.19

Ti Id 2 3F 0.00 0.00 0.00 0.00

Ti s ld 3 SF 0.68 0.68 0.54 0.81
Ti d4 sD 4.53 4.48 4.26 3.35

V Id 3 4F 0.00 0.00 0.00 0.00

V s ld 4 6D 0.28 0.29 0.12 0.25
V dS 6S 3.55 3.55 3.27 2.47

Cr s2d 4 sD 0.00 0.00 0.00 0.00

Cr sld s 7S - 1.09 - 1.06 - 1.27 -1.00
Cr d6 sD 6.08 6.07 5.76 3.40

Mn IdS 6S 0.00 0.00 0.00 0.00

Mn s ld 6 6D 3.50 3.53 3.33 2.14
Mn d7 4F 9.48 9.49 9.15 5.59

Fe Id 6 sD 0.00 0.00 0.00 0.00

Fe s ld 7 SF 2.02 2.06 1.80 0.87
Fe d" 3F 7.85 7.87 7.46 4.07

Co Id 7 4F 0.00 0.00 0.00 0.00

Co sId" 4F 1.79 1.83 1.53 0.42
Co d9 2D 7.48 7.53 7.04 3.36

Ni ld" 3F 0.00 0.00 0.00 0.00

Ni s ld 9 3D 1.57 1.63 1.27 - 0.03
Ni dlO IS 5.95 6.04 5.47 1.71

Cu s2d 9 2D 0.00 0.00 0.00 0.00

Cu sId 10 2S -0.03 0.06 -0.37 - 1.49

TABLE IX. First transition row spin-orbit splittings..

Atom Configuration States AREpb REpc OF' Expte

K pI 2PI/2-2P3/2 38 47 48 58
Ca+ pI 2P I/2-2P3/ 2 172 198 203 223
Sc dl 2D312-2Ds/2 146 143 174 168
Ti+ dl 2D3/2-2DS/2 350 389 400 232
Tj3+ dl 2D31r2Ds/2 374 421 434 384
Cu d9 2Ds 12-2D312 1875 1878 2140 2043
Zn+ d9 2Ds/2-2D 312 2477 2513 2833 2719
Ga pI 2P I/2-2P312 811 779 803 826
Ge+ pI 2P I/2-2P312 1806 1756 1779 1767
Br pS 2P312-2P112 3963 3828 3762 3684
Kr+ pS 2P312-2PI12 5691 5543 5470 5371

aem-I,
bFirst-order splitting due to AREP wave functions with n so determined using REP's and two-component
spinors.
C Energy difference between the respective states using numerical REP's and basis sets of two-component spin-

ors.
d Results obtained using the Dirac-Fock program of J. P. Desclaux, Ref. 7 (frozen core, excluding Breit correc-
tions).
<Reference 13.

J. Chem. Phys., Vol. 84, No. 12. 15 June 1986

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 Hurley et al. : Relativistic effective potentials. II 6853

cases were it not for the importance of relativistic etTects.
The present results indicate that for the first transition row
elements errors due to the etTective potential approximation
may be much smaller than the errors in conventional all-
electron calculations which neglect relativity. Compared to
such work REPs otTer not only increased computational
speed (at least in the integral generation, SCF and integral
transformation steps) but also reliability.
ACKNOWLEDGMENTS
This report is based on work supported in part by the
National Science Foundation under Grant Nos. CHE-
8214689 and CHE-8214665 and also by the Research Cor-
poration.
'L. F. Pacios and P. A. Christiansen, J. Chern. Phys. 82, 2664 (1985).
2p. A. Christiansen, Y. S. Lee, and K. S. Pitzer, J. Chern. Phys. 71, 4445
( 1979).
3y' S. Lee, W. C. Ermler, and K. S. Pitzer,J. Chern. Phys. 67, 5861 (1977).
4p. J. Hay and W. R. Wadt, J. Chern. Phys. 82, 270 (1985); W. R. Wadt
and P.J. Hay, ibid. 82, 284 (1985); P. J. Hay and W. R. Wadt, ibid. 82, 299
(1985).
sR. W. Cowan and D. C. Griffin, J. Opt. Soc. Am. 66, 1010 (1976).
6R. L. Martin and P. J. Hay, J. Chern. Phys. 75, 4539 (1981).
7J. P. Desc1aux, Cornput. Phys. Cornrnun. 9, 31 (1975).
BW. C. Ermler, Y. S. Lee, P. A. Christiansen, and K. S. Pitzer, Chern. Phys.
Lett. 81, 70 (1091).
9L. R. Kahn, P. Baybutt, and D. G. Truhlar, J. Chern. Phys. 65, 3826
(1976).
lOA. J. H. Wachters, J. Chern. Phys. 52,1033 (1970).
liP. J. Hay, J. Chern. Phys. 66,4377 (1977).
'2E. C. Walker, L. F. Pacios, and P. A. Christiansen (in preparation).
13C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. Circ. 467 (U. S.
GPO, Washington, D.C., 1949, 1952), Vols. I and II.
'4R. B. Ross, W. C. Ermler, and P. A. Christiansen, J. Chern. Phys. 84, 3297
(1986).
'SW. Muller, J. Flesch, and W. Meyer, J. Chern. Phys. 80, 3297 (1984).

J. Chern. Phys., Vol. 84, No. 12, 15 June 1986

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