Atomic Screening Constants from

SCF Functions. II. Atoms with 37 to 86

Electrons
Cite as: J. Chem. Phys. 47, 1300 (1967); https://doi.org/10.1063/1.1712084
Submitted: 10 April 1967 • Published Online: 03 May 2004

E. Clementi, D. L. Raimondi and W. P. Reinhardt

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J. Chem. Phys. 47, 1300 (1967); https://doi.org/10.1063/1.1712084 47, 1300

© 1967 American Institute of Physics.

 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 41, NUMBER 4 15 AUGUST 1961

Atomic Screening Constants from SCF Functions. II. Atoms with 37 to 86 Electrons
E. CLEMENTI, D. L. RAIMONDI, AND W. P. REINHARDT*
IBM San Jose Research Laboratory, San Jose, California
(Received 10 April 1967)

Minimal basis-set atomic functions for the ground-state atoms from Rb(Z=37) to Rn(Z=86) are
presented. These functions are analyzed in order to obtain systematic data for the screening constants and
atomic radii following the work initiated by Slater.

1. INTRODUCTION II, RESULTS

In a previous paperl (hereafter referred to as I), A. Total Energies and Orbital Exponents
self-consistent-field functions were computed with a
minimal basis set of Slater-type orbitals for atoms with Table I lists atomic number (Z), atomic symbol,
2 to 36 electrons. From the analysis of the optimized outer-shell configuration, electronic state, and the total
orbital exponents, atomic screening constants were
derived for the 1s, 2s, 2p, 3s, 3p, 4s, 3d, and 4p electrons. TABLE I. Total energy for neutral atoms from Rb through Xe.
The screening constants were compared with those
Z Atom Configuration State Energy
proposed by Slater in his classical work2 and the new
"rules" were obtained. The previous work was moti- 37 Rb 5s(1) 2S -2930.6932
vated by the need for simple wavefunctions to com- 38 Sr 5s(2) 'S -3123.7176
plement the large number of highly accurate wave- 39 Y 4d(1) 2D -3324.7806
functions available for the first-, second-, and third-row 40 Zr 4d(2) 3F -3531.3152
atoms. For the atoms of the fourth, fifth, and sixth rows 41 Nb 4d(3) 4F -3745.4783
the need for simple wavefunctions is even more ap- 41 Nb- 5s(1) 4d(4) 6D -3745.2448
42 Mo 4d(4) 5D -3967.0362
parent, since little data is presently available. They are
42 Mo- 5s(1) 4d(5) 7S -3966.3422
particularly useful where preliminary computations are 6S
43 Tc 4d(5) -4196.0510
desired or where high accuracy is either not feasible 44 Ru 4d(6) aD -4432.3593
with present techniques or not required. In this paper, 44 Ru- 5s(1) 4d(7) 5F -4432.1106
we give SCF minimal basis-set functions for atoms with 45 Rh 4d(7) 4F -4676.2624
37 to 86 electrons or for the atoms from rubidium to 45 Rh- 5s(1) 4d(8) 4F -4676.0290
radon in the periodic table. In addition, the previous 46 Pd 4d(8) 3F -4927.8059
results are combined with the present data in discussing 46 Pd- 5s(0) 4d(1O) 'S -4927.1726
screening constants and orbital radii. In order to clarify 47 Ag 4d(9) 2D -5187.0706
the results to be presented, a short review of the theory 47 Ag- 5s(1) 4d(10) 2S -5186.8939
follows. 48 Cd 4d(1O) 'S -5454.1909
49 In 5p(1) 2p -5729.0988
The Slater-type basis set has the form 3p
50 Sn 5p(2) -6011.6722
Xn,I,m=Nr n- l exp( -tn,l,mr) Y I,m(8, I{J), (1) 51 Sb 5p(3) 4S -6302.0043
52 Te 5p(4) 3p -6600.0386
where n, l, and m are the usual quantum numbers, Y l m 53 I 5p(5) 2p -6905.9462
is a spherical harmonic, N is a normalization factor, arid 54 Xe 5p(6) 'S -7219.7921
t n,l.m is the orbital exponent related to the screening
constant Un,l.m and to the effective nuclear charge Zeff - The filling up of the electronic shells is not exactly consecutive for the
ground states of the fourth-row atoms. Therefore. for the fourth-row atoms
by the relations we have given two states: the lowest one and that which one would obtain
if the filling up of the shell would be regular.
tn,I,m=Zeff/n= (Z-Un,l,m)/n. (2)
It should be noted that we use integer values for "n" energy for atoms from rubidium to xenon. Table II
whereas Slater used either integer values (in the first- lists the optimized orbital exponents for the same group
and second-row elements) and fractional values in the of atoms. Tables III and IV similarly apply to the atoms
third and higher rows of elements. from cesium to radon. It is noted that the 4f electrons
* Present address: Harvard University, Chemistry Department, are not well described by a single Slater-type orbital
Cambridge, Mass. when the number of 4f electrons is small. This is attrib-
1 E. Clementi and D. L. Raimondi, J. Chern. Phys. 38, 2686
(1963) .
uted to the extreme broadness of the 4f orbital. Con-
2 J. C. Slater, Phys. Rev. 36, 57 (1930). siderable trouble was involved in obtaining results for
1300
 ATOMIC SCREENING CONSTANTS. II 1301

TABLE II. Tabulation of optimized orbital exponents for neutral Rb through neutral Xe in their ground state.

Z Atom Is 2$ 2p 3$ 3p 4s 3d 4p 5s 4d 5p

37 Rb 36.2078 13.5784 16.5194 7.2809 7.1011 3.0970 7.2264 2.7202 0.9969

38 Sr 37.1911 13.9509 17.0152 7.5546 7.3892 3.3611 7.5754 2.9830 1. 2141
39 Y 38.1756 14.3111 17.5016 7.8505 7.6975 3.5659 8.4657 3.1864 1.2512 3.9896
40 Zr 39.1590 14.6869 17.9964 8.1205 7.9485 3.7254 8.5223 3.3650 1.2891 3.2679
41 Nb 40.1423 15.0626 18.4911 8.3905 8.2184 3.9090 8.7847 3.5652 1.3392 3.0796
41 Nb a 40.1423 15.0626 18.4911 8.3905 8.2052 3.8207 8.7490 3.5211 1.1842 2.8094
42 Mo 41.1256 15.4384 18.9859 8.6605 8.5030 4.1037 9.1097 3.7622 1.3952 3.1110
42 Mo· 41.1256 15.4384 18.9859 8.6605 8.4912 4.0241 9.0761 3.7442 1.2212 2.8481
43 Tc 42.1090 15.8141 19.4704 8.9304 8.7947 4.2996 9.4510 3.9528 1.4453 3.2205
44 Ru 43.0923 16.1899 19.9754 9.2004 9.0844 4.4876 9.7981 4.1291 1.4905 3.3470
44 Ru· 43.0923 16.1899 19.9754 9.2004 9.0737 4.4140 9.7863 4.1087 1.2969 3.2032
45 Rh 44.0756 16.5656 20.4702 9.4704 9.3724 4.6571 10.1478 4.3236 1.5286 3.4937
45 Rh- 44.0756 16.5773 20.4702 9.4795 9.3848 4.6454 10.1350 4.2849 1.3279 3.3606
46 Pd 45.0589 16.9414 20.9650 9.7404 9.6616 4.8568 10.4989 4.5010 1.5675 3.6476
46 Pd- 45.0589 16.9414 20.9650 9.7404 9.6732 4.7465 10.4837 4.4308 3.4044
47 Ag 46.0423 17.3171 21.4597 10.0104 9.9476 5.0398 10.8503 4.6777 1.6057 3.8064
47 Ag- 46.0423 17.3171 21.4597 10.0104 9.9362 4.9662 10.8466 4.6406 1.3511 3.6907
48 Cd 47.0256 17.6929 21.9545 10.2804 10.2305 5.2173 11.2023 4.8528 1.6384 3.9692
49 In 48.0097 18.0618 22.4490 10.5436 10.5069 5.4403 11.5594 5.0922 1.9023 4.2354 1.6940
50 Sn 48.9920 18.4297 22.9427 10.8066 10.7844 5.6645 11.9139 5.3163 2.1257 4.4925 1.8204
51 Sb 49.9744 18.7977 23.4363 11.0697 11.0613 5.8859 12.2666 5.5453 2.3222 4.7436 1.9989
52 Te 50.9568 19.1656 23.9300 11.3327 11.3363 6.1021 12.6131 5.7805 2.5076 4.9900 2.1617
53 I 51.9391 19.5335 24.4237 11.5958 11.6138 6.3243 12.9669 6.0074 2.6807 5.2335 2.3223
54 Xe 52.9215 19.9015 24.9173 11.8588 11.8892 6.5432 13.3156 6.2393 2.8436 5.4733 2.4849
• These atoms have configurations corresponding to atoms labeled "au of Table I.

TABLE III. Total energy for neutral atoms from Cs through Rn the atoms from lathanum (Z =57) to promethium
(in atomic units) .
(Z = 60). In fact, for La, Pr, Nd, and Pm 2 STO's were
Z Atom Configuration State Energy required to get convergency. In Table IV these cases are
apparent by the use of a second 4f STO (labeled 41').
55 Cs 6$(1) 2S 7541.3432 In each case the first 4j STO given is the dominant one.
56 Ba 6s(2) IS 7870.6740 In the case of La and Ce the extremely small orbital
57 La 4/(1) 2F - 8207.7052
3[
exponent indicates the diffusiveness of the 4f electron,
58 Ce 4f(2) - 8552.4491
59 Pr - 8905.3989
since the orbital exponent is inversely proportional to
4f(3) 4J
60 Nd 4/(4) 6[ - 9267.0675 the radius of maximum charge density.
61 Pm 4f(5) GH - 9637.0680 B. Screening Constants and Orbital Radii
62 Sm 4/(6) 7F -10015.325
63 Eu 4/(7) 8S 10402.457 The screening constants reported in F were presented
64 Gd 4f(8) 7F -10797.853 with the following qualifications. If one wishes to
65 Tb 4/(9) 6H -11 202.707 identify the u's with the f's via Eq. (2), then one should
66 Dy 4/(10) 5[ -11 615.016 restrict himself only to those orbitals which have no
67 Ho 4/(11) 4J -12038.572 other orbital of the same symmetry in the atom. For
68 Er 4/(12) 3[ -12467.338 example, if one considers the neon atom, the corre-
69 Tm 4f(13) 2F -12907.267 spondence between f and u is unambiguous for the 2p
70 Yb 4f(14} IS -13 356.155
2D
but not for the 1s and 2s orbitals. The reason is simply
71 Lu 5d(1) -12816.567
72 Hf 5d(2) 3F -14285.319
that the complete basis set of a given symmetry is used
73 Ta 5d(3) 4F -14763.336 in building the orbitals of that symmetry.
74 W 5d(4) 5D -15250.513 In other words, as noted in I, the coupling of the
75 Re 5d(5) 'S 15746.921 vectors for the basis set of a given symmetry prevents
76 Os 5d(6) 6D -16252.392 an objective division of various contributions to the
77 Ir Sd(7) 'F -16767.183 screening constants. The problem becomes clearly more
78 Pt 5d(8) SF -17291.316 acute the larger the basis set of a given symmetry. In
79 Au 5d(9) 2D -17824.845 Fig. 1, the screening constants calculated from Eq. (2)
80 Hg 5d(10) IS -18367.869 are plotted versus atomic number for the atoms from
81 Tl 6p(l) 2p -18920.276
ap helium to radon. Certainly, discontinuities should exist
82 Pb 6p(2) -19481.953
83 Bi 6p(3) 4S -20052.992
where new orbitals begin to fill, and these are evident.
84 Po 6p(4) .p -20633.317 But a detailed discussion of these results is clouded by
85 As 6p(5) 2p -21223.079 the ambiguities discussed above. There is a simple way
86 Rn 6p(6) IS -21822.323 by which these ambiguities may be in part removed. Let
us consider again the neon atom. In the minimal basis
 .......
CN
o
N

T ABLE IV. Tabulation of optimized orbital exponents for neutral Cs through neutral Rn in their ground state.

Z Atom Is 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p 6s 4/ 4/' 5d 6p

55 Cs 53.9043 20.2558 25.4098 12.1258 12.1926 6.7606 13.6602 6.4644 3.0889 5.7096 2.7302 1.0605
(')
56 Ba 54.8861 20.6234 25.9048 12.3852 12.4388 6.9800 14.0081 6.7008 3.3239 5.9460 2.9601 1.2625
57 La 55.8683 20.9767 26.3978 12.6477 12.7132 7.1991 14.3534 6.9266 3.5622 6.1813 3.1792 1.5520 0.3400 3.5230 t-<
tr1
58 Ce 56.8481 21.3700 26.8912 12.8864 12.9865 7.4200 14.6951 7.1516 3.7827 6.4152 3.3931 1.7994 0.4190
59 Pr 57.8306 21. 7310 27.3847 13.1670 13.2748 7.5833 15.0508 7.2642 3.5226 6.5743 3.0567 1.2911 5.2752 0.5000 ~
60 Nd 58.8132 22.1081 27.8783 13.4476 13.5630 7.7466 15.3856 7.5035 3.7485 6.7023 3.3922 1.5511 5.5665 0.5800 tr1
61 Pm 59.7958 22.4852 28.3719 13.7282 13.8513 7.9099 15.6994 7.6558 3.7671 6.9350 3.2828 1.5659 5.7835 0.6500 Z
62
63
8m
Eu
60.7783
61.7609
22.8674
23.2354
28.8655
29.3590
14.0088
14.2894
14.1395
14.4280
8.0731
8.2170
16.0763
16'.4176
7.7720
7.9687
3.6498
3.7180
7.0599
7.2352
3.2562
3.3110
1.3353
1.3536
5.8829
6.0800
....>-3
64 Gd 62.7435 23.6085 29.8527 14.5699 14.7164 8.3610 16. 75J)0 8.1617 3.7764 7.4084 3.3528 1.3691 6.2534 :;0
65 Tb 63.7261 23.9861 30.3462 14.8505 15.0049 8.5050 17.0995 8.3497 3.8341 7.5775 3.3922 1.3834 6.4662 ;;.-
66 Dy 64.7086 24.3547 30.8398 15.1311 15.2935 8.6480 17.4433 8.4565 3.8608 7.7545 3.4254 1.3906 6.6340 ....
67 Ho 65.6912 24.7278 31.3334 15.4117 15.5818 8.8280 17.7823 8.6407 3.9152 7.9179 3.4678 1.4065 6.8674 ~
68 Er 66.6737 25.1008 31.8270 15.6923 15.8703 9.0580 \8.1201 8.7773 3.9436 8.0678 3.4944 1.4127 6.9946 0
69 Tm 67.6563 25.4739 32.3206 15.9728 16.1587 9.2844 18.4581 8.9970 4.0074 8.2360 3.5456 1.4307 7.1585 Z
70 Yb 68.6389 25.8470 32.8142 16.2534 16.4455 9.3794 18.7989 9.1005 4.0300 8.3974 3.5663 1.4322 7.3580 t:I
71 Lu 69.6195 26.2249 33.3055 16.5115 16.7221 9.5673 19.1396 9.2976 4.1910 8.8223 3.7360 1.4674 7.7328 4.0226 .....
72 Hf 70.6016 26.5949 33.7994 16.7705 16.9944 9.7443 19.4766 9.4824 4.3666 8.8810 3.9170 1.5274 8.0524 3.3239
73 Ta 71. 5837 26.9649 34.2932 17.0305 17.2668 9.9397 19.8137 9.6837 4.5387 9.0810 4.0947 1.5875 8.3676 3.2736 ;;.-
74 W 72.5657 27.3349 34.7871 17.2900 17.5392 10.1397 20.1508 9.8871 4.7083 9.2933 4.2651 1.6424 8.6777 3.3484 Z
75 Re 73.5478 27.7049 35.2810 17.5495 17.8115 10.3391 20.4849 10.0933 4.8714 9.5136 4.4288 1.6860 8.9812 3.4766 t:I
76 Os 74.5299 28.0749 35.7749 17.8091 18.0839 10.5238 20.8249 10.2860 5.0190 9.7145 4.5820 1.7205 9.2882 3.5994 :;0
77 Ii- 75.5119 28.4449 36.2688 18.0686 18.3563 10.7120 21.1620 10.4785 5.1691 9.9343 4.7322 1.7611 9.5862 3.7392 tr1
78 Pt 76.4940 28.8149 36.7627 18.3281 18.6287 10.9097 21.4991 10.6826 5.3176 10.1575 4.8839 1. 7919 9.8765 3.8815 ....
79 Au 77.4761 29.1849 37.2566 18.5876 18.9010 11.1033 21. 8361 10.8867 5.4655 10.3820 5.0340 1.8230 10.1624 4.0253 Z
80 Hg 78.4581 29.5547 37.7505 18.8471 19.1734 11.3112 22.1732 11.1015 5.6222 10.6170 5.1934 1.8589 10.4402 4.1712 ::r:
81 TI 79.4409 29.8421 38.2431 19.1397 19.4555 11.5197 22.5114 11.3042 5.8244 10.8472 5.4177 2.1366 10.7169 4.4050 2.0423 ;;.-
82 Pb 80.4195 30.2150 38.7383 19.3841 19.7165 11.7232 22.8489 11.5084 6.0263 11.0799 5.6060 2.3500 10.9922 4.6304 2.0655 :;0
83 Bi 81.3982 30.5880 39.2335 19.6285 19.9774 11.9268 23.1805 11.7126 6.2058 11.3098 5.8042 2.5400 11.2673 4.8488 2.2233 t:I
84 Po 82.3768 30.9609 39.7286 19.8729 20.2383 12.1304 23.5240 11.9168 6.4046 11.9168 6.0049 2.7218 11.5396 5.0608 2.3701 >-3
85 As 83.3554 31.3338 40.2238 20.1173 20.4992 12.3339 23.8615 12.1210 6.5867 11.7624 6.2080 2.8833 11.8101 5.2678 2.5272
86 Rn 84.3341 31.7068 40.7190 20.3617 20.7602 12.5375 24.1991 12.3253 6.7786 11.9857 6.3942 3.0540 12.0828 5.4706 2.6793
 ATOMIC SCREENING CONSTANTS. II 1303

70 j 6P
68 65
66
64
62
60
58
56
( 5d

54
52
50
);;;:= 5p
55

~J!
48
b
46
f-
z 44
~

('4f
(f)
z 42
0 5p
u 40 -
<!)
z 38 4f
4d

/~;::/::
z 36 --
w
w
cr 34
u
(f) / .......
32 - 55
30
28-
26
24-
4p
/
/y 35
3p

~~
4d 25
22
20
18
16 45
14 3d
3d
12
10
35 3p
8
6
2p
4
25
2 2p I s
Is
0
0 5 10 20 30 40 50 60 70 80 90
Z ---.

FIG. 1. The screening constants IT calculated from Eq. (2) are plotted vs atomic number Z.

set-SCF formalism, we use one is STO, one 2s STO, Therefore, one can obtain two sets of s-'s. The first set
and one 2p STO. The radial part of the SCF orbital, contains the r's which correspond to the optimized
f(r) , is characterized by the value of r for which rf(r) minimal basis set. The second set contains the r's which
has an extrema or a node. If the minimal basis set is correspond to STO's, not used in the computation, but
well optimized the extrema and nodes are unambigu- which have the same rmax as given by the first set. Since
ously determined by plotting the radial functions. the minimal basis set of STO's gives an orthogonal set
1304 CLEMENTI, RAIMONDI, AND REINHARDT

0.8

0.6
;:;
.;

~
""E 0.4

0.2

5.8 0.0
65
60 70
z __80 90
5.4

5.0 55

45
4.6

4.2
...,
:::J

.!i.
)(
3.8
~E" 35

3.4
25
3.0
2.8
~ 6p
4p
2.4
3p \ \ 6p

2.0 65

1.8
2p

1.4

1.0 5d
5p
.8
.6
:4

.2j__~~~=;~~~~~~~~~~~~~~~~~~~~I:N~SE~R~T:-__-1
.0
o 10 20 30 40 50 60 70 80 90
Z---..
FIG. 2. Radii of maximum charge density rmax are plotted vs atomic number Z.

of SCF orbitals and since the STO's are nodeless func- neon atom, the minimal basis set is
tions, the only rmax of rj(r) which should be considered
1s(SCF) =f(rlB) Y oo = 0.99735x (1s) +O.01092x(2s) ,
is that corresponding to the main and outermost lobe
from the nucleus. This presents no ambiguity since the 2s(SCF) =j(r28) Yoo= -O.25499x(1s) +1.02937x(2s) ,
main lobe is distinct from the orthogonality lobes of the
SCF orbitals. For example, using again the case of the 2p(SCF) =f(2p) Y lm =X2p, (3)
 ATOMIC SCREENING CONSTANTS. II 1305

r--
He
0.31

Li Be B C N 0 F Ne
1.67 1.12 0.87 0.67 0.56 0.48 0.42 0.38

Na Mg Al Si P S CI Ar
1. 90 1.45 1.18 1.11 0.98 0.88 0.79 0.71

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br KT
2.43 1.94 1.84 1.76 1.71 1.66 1.61 1.56 1.52 1.49 1:45 1. 42 1.36 1.25 1.14 1.03 0.94 0.88

Rb Sr Y Zr Nb Mo r..:.,c Ru Rh Pd Ag Cd In Sn Sb Te I Xe
2.65 2.19 2.12 2.06 1. 98 1.90 1.83 1.78 1. 73 1.69 1.65 1.61 1.56 1.45 1. 33 1.23 1.15 1. 08

Cs Ba La Hf Ta W Re Os Ir Pt Au Eg TI Pb Bi Po At Rn
2.98 2.53 (6.22) 2.08 2.00 1.93 1. 88 1. 85 1. 80 1. 77 1.74 1.71 1.56 1.54 1.43 1. 35 1. 27 1. 20

I Ce I Pr I Nd I Pm I Sm I Eu I Gd I Tb I:
(5.05) 2.47 2.06 2.05,2.38 2.31 2.33 2.25 Dy
2.28 I go I Er I Tm
2.26 2.26 2.22 I I I
Yb
2.22 Lu
2.17

FIG. 3. Atomic radii (Angstroms), determined from minimal-basis-set SCF functions.

where x(ls), x(2s), and x(2p) are normalized STO's where the number of STO's of the same symmetry is
with orbital's exponents equal to 9.6421,2.8793, and small. However, the differences will be considerably
2.8792, respectively. From rf(r)max one would obtain greater for atoms with large numbers of electrons.
the following set of f's: In addition to the usefulness of the orbital radii
maxima for the screening constant analysis, these data
f(ls) =9.6339, are interesting in themselves for consideration of atomic
S-'(2s) =2.7933,
radii. Certainly, there is a correlation between atomic
radii and the radius of maximum charge density in the
f(2p) =2.8792, (4) outermost shell of the atom. In a recent paper, Slater3
has found a good correlation between his empirically
which is different than the set used in the computation determined radii and radii calculated from the wave-
of the SCF function. Since we are using minimal basis functions of Liberman, Waber, and Cromer. 4 •5 Thus, in
sets, the difference will not be too large for those cases Fig. 2 we give radii of maximum charge density for each

TABLE V. Comparison of Roo .. for rare-gas atoms determined by using SCF functions of varying basis-set dimension (in atomic units).

Basis
Atom set Is 2s 2p 3s 3p 4s 3d 4p 5s 4d 5p
He AI 0.593
He B6 0.568
He C6 0.569
Ne Al 0.104 0.716 0.695
Ne Be 0.103 0.687 0.623
Ne C6 0.103 0.683 0.635
Ar Al 0.057 0.346 0.286 1. 23 1.35
Ar B6 0.057 0.338 0.280 1.18 1.30
Ar C6 0.057 0.339 0.280 1.18 1.30
Kr AI 0.028 0.162 0.126 0.489 0.471 1.46 0.436 1.66
Kr B6 0.028 0.158 0.126 0.476 0.469 1.37 0.408 1.56
Kr C6 0.028 0.158 0.125 0.475 0.467 1.38 0.412 1.57
Xe A 0.019 0.106 0.081 0.301 0.279 0.700 0.227 0.710 1.81 0.760 2.04
Xe B" 0.018 0.102 0.080 0.291 0.279 0.687 0.225 0.705 1. 74 0.752 1.96
A, Single zeta.
B, Double zeta.
C, Hartree-Fock.

" Preliminary results of Clementi.

3 J. C. Slater, J. Chern. Phys. 41, 3199 (1964).

(D. Liberman, J. T. Waber, and D. T. Cromer, Phys. Rev. 137, A27 (1965).
Ii J. Waber and D. T. Cromer, J. Chern. Phys. 42, 4116 (1965) j see in addition, C. Froese, J. Chem. Phys.45, 1417 (1966).
 1306 CLEMENTI, RAIMONDI, AND REINHARDT

70 f6 P
68 65
66
64
62
60
5d
58
56 5p
55
54
52
50
48
-b 46
I- 44 45
z 4p
« 42
I-
en 4d
z 40
0
(.)

<!)
38 4f
z
z 36
w 35
W 34
0:
(.)
en 32
30 3p

28
26
4p 25
24
22
20
18
16
14 3d
12
10
8 3s

6
4
25 --- 2p

2 2p
15 Is
0
0 10 20 30 40 50 60 70 80 90
Z-.
FIG. 4. The screening constants u' calculated from "mn are plotted vs atomic number Z.

of the orbitals for atoms from helium to radon, and in atomic number are relatively smooth. The contraction
Fig. 3 the atomic radii in angstroms are given for of the d and f orbitals is certainly evident in the Fig. 2
helium to radon as calculated from the minimal-basis- insert. Due to the qualitative nature of these simple
set wavefunctions described above. Apart from some wavefunctions, a detailed discussion of these results is
peculiarities, notably the behavior of the 6s orbital as postponed until a similar analysis is made on the more
the 4j shell is being filled, the variations with increasing accurate wavefunctions which are available for atoms
 ATOMIC SCREENING CONSTANTS. II 1307

from helium to xenon. This is exemplified in Table V electrons. Because of the contraction of the 4f, 4d, and
where we have compared orbital radii for the rare gas 4p orbitals the screening constants for these orbitals
atoms (helium, neon, argon, krypton, and xenon) as should in the limit of high Z be less than the screening
determined from wavefunctions of varying basis set constant for the 4s orbital. Considering radon, in Fig. 1
dimensions.6 In the outer shells, large deviations are the order of increasing values of the screening constants
evident. are 4s, 4p, 4f, and 4d. But in Fig. 4, we have similarly
In Fig. 4 we have plotted the screening constants 4f, 4d, 4p, and 4s which is the correct description. Again
determined from the orbital radii by the technique a more detailed analysis is postponed until this analysis
described above. Although the trends are similar, these can be applied to more accurate wavefunctions.
data are not clouded by the coupling of the vectors of So that all the data is available to the reader, tables of
orbitals of the same symmetry. One difference which orbital radii for the atoms from helium through radon
stands out is the screening of the 4s, 4p, 4d, and 4f are available upon request to the authors.7
7 E. Clementi, D. L. Raimondi, and W. P. Reinhardt, IBM Res.
6 E. Clementi, IBM J. Res. and Develop. Supp\. 9, 2 (1965). Rept. RJ-431.

THE JOURNAL OF CHEMICAL PHYSICS VOLUME 47, NUMBER 4 15 AUGUST 1967

Temperature Dependence, Orientation Correlation, and Molecular Fields in

Second-Harmonic Light Scattering from Liquids and Gases
D. L. WEINBERG*

Lincoln Laboratory,t Massachusetts Institute of Technology, Lexington, Massachusetts

(Received 3 January 1967)

The properties of second-harmonic light scattering in fluids are derived in terms of the molecular polari-
zabilities, orientation correlation among molecules, and the molecular field Fa. Measurements of scattering
intensity in CCl4 and water, from about 10° to 60°C, are reported. The variations with temperature, and
therefore apparently the effects of changes of orientation correlation, are slight. The influence of preferred
orientation in CCI 4, of the type deduced from x-ray diffraction, is calculated. The third-rank molecular
polarizability tensor consists of a fourth-rank tensor contracted with Fa, in addition to the term previously
known, which is independent of Fa. With Fa arising from molecular multipole moments, the new term
explains some measured depolarizations in liquids, and accounts for the spectral line, but not the back-
ground, observed in methane gas. In the case of molecular dipole moments, the new term can cause spectral
narrowing.

1. INTRODUCTION each other, such as harmonic generation and stimulated

eIffiSSlOn.
Second-harmonic light scattering has been observed
The formulation which Buckingham and Stephen3
in liquids and fused quartzl and methane gas. 2 When
(BS) applied to Rayleigh scattering is used. Let the
an optical electric field of angular frequency w is incident
dipole moment of an isolated molecule in an electric
on matter, Rayleigh scattering arises from local, e.g., field Ga be
molecular, induced electric dipoles, (neglecting higher-
order induced moments) radiating independently of Pa=j.la+cxa,sC/l+Ma/l·P/lG'Y+ha/l'YoGflGrGo+·"". (1)
each other at the fundamental frequency w. Second-
harmonic scattering is related, but the nonlinear re- This can be applied to a molecule in a fluid, where
sponse at 2w is pertinent. Raman scattering differs Ga=Ea+la+Fa, if the fields are sufficiently homo-
from both, in that the scattered light differs from a geneous. Ea is the optical field in the medium, Ea+la
harmonic of w by a natural frequency of the medium. is the local optical field, and Fa is the field with no
Finally there are effects in which the local dipoles incident light beam. (The present I a+F a is the Fa of
oscillate coherently, i.e., in definite phase relations with BS.) Since 2w is well below the frequencies of the
strong absorption bands in the cases to be considered,
* Present address: NASA Electronics Research Center, Cam- the polarizability tensors are approximately symmetri-
bridge, Mass. cal in all pairs of indices. They will be assumed to be
t Operated with support from the U.S. Air Force. exactly so. Table I relates the elements of f3a/l'f and of
1 R. W. Terhune, P. D. Maker, and C. M. Savage, Phys. Rev.
Letters 14, 681 (1965). 'Ya/l'Yo for some molecules of interest here.
2 P. D. Maker, Physics of Quantum Electronics, P. L. Kelley,
B. Lax, and P. E. Tannenwald, Eds. (McGraw-Hill Book Co., 3 A. D. Buckingham and M. J. Stephen, Trans. Faraday Soc.
New York, 1966), p. 60. 53, 884 (1957), BS.