A systematic quantum Monte Carlo study of 2p atoms (C, N, O) and 3p atoms (Si, P, S) is performed to investigate the influence of correlation on the interpretation of Hund’s multiplicity rule, which is an extension of our previous study of the carbon atom [J. Chem. Phys.121, 7144 (2004)] to heavier atoms. The accuracy in the present study is significantly improved as compared with the previous study. A detailed analysis of the correlation contribution to individual energy components of the total energy is given beyond the self-consistent Hartree-Fock calculation. The stability of the highest spin-multiplicity state of all the atoms is ascribed to the greater electron-nucleus attraction energy that is gained at the cost of increasing the electron-electron repulsion energy as well as the kinetic energy. The present study demonstrates that correlation does not change the above conclusion due to the Hartree-Fock theory to support Boyd’s less screening mechanism.

1.
K.
Hongo
,
R.
Maezono
,
Y.
Kawazoe
,
H.
Yasuhara
,
M. D.
Towler
, and
R. J.
Needs
,
J. Chem. Phys.
121
,
7144
(
2004
).
2.
R. J.
Boyd
,
Nature (London)
310
,
480
(
1984
).
3.
F.
Hund
,
Z. Phys.
33
,
345
(
1925
);
F.
Hund
,
Z. Phys.
34
,
296
(
1925
);
Linienspektren und periodisches System der Elemente
(
Springer-Verlag OHG
,
Berlin
,
1927
).
4.
I. N.
Levine
,
Quantum Chemistry
, 5th ed. (
Prentice Hall
,
New Jersey
,
1999
).
5.
J. C.
Slater
,
Phys. Rev.
34
,
1293
(
1929
);
Quantum Theory of Atomic Structure
(
McGraw-Hill
,
New York
,
1960
), Vol.
I
.
6.
E. R.
Davidson
,
J. Chem. Phys.
41
,
656
(
1964
);
E. R.
Davidson
,
J. Chem. Phys.
42
,
4199
(
1965
).
7.
R. P.
Messmer
and
F. W.
Birss
,
J. Phys. Chem.
73
,
2085
(
1969
).
8.
S.
Fraga
,
J.
Karwouski
, and
K. M. S.
Saxena
,
Handbook of Atomic Data
(
Elsevier
,
Amsterdam
,
1976
).
9.
J. P.
Colpa
,
A. J.
Thakkar
,
V. H.
Smith
, Jr.
, and
P.
Randle
,
Mol. Phys.
29
,
1861
(
1975
).
10.
J.
Katriel
,
Theor. Chim. Acta
23
,
309
(
1972
).
11.
J.
Katriel
and
R.
Pauncz
,
Adv. Quantum Chem.
10
,
143
(
1977
).
12.
A.
Lemberger
and
R.
Pauncz
,
Acta Phys. Acad. Sci. Hung.
27
,
169
(
1969
).
13.
R. J.
Boyd
and
C. A.
Coulson
,
J. Phys. B
6
,
782
(
1973
);
R. J.
Boyd
and
C. A.
Coulson
,
J. Phys. B
7
,
1805
(
1974
).
14.
K. V.
Darvesh
and
R. J.
Boyd
,
J. Chem. Phys.
87
,
5329
(
1987
);
K. V.
Darvesh
and
R. J.
Boyd
,
J. Chem. Phys.
90
,
5638
(
1989
).
15.
K. V.
Darvesh
,
P. D.
Fricker
, and
R. J.
Boyd
,
J. Phys. Chem.
94
,
3480
(
1990
).
16.
K. V.
Darvesh
,
P. D.
Fricker
, and
R. J.
Boyd
,
Chem. Phys.
157
,
99
(
1991
).
17.
G.
Marc
and
W. G.
McMillan
, in
Advances in Chemical Physics
, edited by
I.
Prigogine
and
S. A.
Rice
(
Wiley
,
New York
,
1985
), Vol.
58
, pp.
209
361
.
18.
W. M. C.
Foulkes
,
L.
Mitas
,
R. J.
Needs
, and
G.
Rajagopal
,
Rev. Mod. Phys.
73
,
33
(
2001
).
19.
J. B.
Anderson
,
J. Chem. Phys.
65
,
4121
(
1976
).
20.
P. J.
Reynolds
,
D. M.
Ceperley
,
B. J.
Alder
, and
W. A.
Lester
, Jr.
,
J. Chem. Phys.
77
,
5593
(
1982
).
21.
D. M.
Ceperley
and
M. H.
Kalos
, in
Monte Carlo Methods in Statistical Physics
, edited by
K.
Binder
(
Springer
,
Berlin
,
1979
), pp.
145
194
.
22.
R. J.
Jastrow
,
Phys. Rev.
98
,
1479
(
1955
).
23.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
 et al, GAUSSIAN 98, Rev. A.11.1, Gaussian Inc., Pittsburgh, PA,
2001
.
24.
N. D.
Drummond
,
M. D.
Towler
, and
R. J.
Needs
,
Phys. Rev. B
70
,
235119
(
2004
).
25.
T.
Kato
,
Commun. Pure Appl. Math.
10
,
151
(
1957
).
26.
A. J.
Williamson
,
S. D.
Kenny
,
G.
Rajagopal
,
A. J.
James
,
R. J.
Needs
,
L. M.
Fraser
,
W. M. C.
Foulkes
, and
P.
Maccallum
,
Phys. Rev. B
53
,
9640
(
1996
).
27.
C. J.
Umrigar
,
K. G.
Wilson
, and
J. W.
Wilkins
,
Phys. Rev. Lett.
60
,
1719
(
1988
).
28.
P. R. C.
Kent
,
R. J.
Needs
, and
G.
Rajagopal
,
Phys. Rev. B
59
,
12344
(
1999
).
29.
R. J.
Needs
,
M. D.
Towler
,
N. D.
Drummond
, and
P. R. C.
Kent
, CASINO version 1.7 User Manual,
University of Cambridge
, Cambridge, (
2004
).
30.
G.
Gaigalasa
and
C. F.
Fischer
,
Comput. Phys. Commun.
98
,
255
(
1996
).
31.
S. J.
Chakravorty
,
S. R.
Gwaltney
,
E. R.
Davidson
,
F. A.
Parpia
, and
C. F.
Fischer
,
Phys. Rev. A
47
,
3649
(
1993
).
32.
Atomic spectra database, Version 3.0,
National Institute of Standards and Technology
(
2005
); URL: http://physics.nist.gov/PhysRefData/ASD/
33.
A.
Ma
,
N. D.
Drummond
,
M. D.
Towler
, and
R. J.
Needs
,
Phys. Rev. E
71
,
066704
(
2005
).
34.
F. J.
Gálvez
,
E.
Buendía
, and
A.
Sarsa
,
J. Chem. Phys.
124
,
044319
(
2006
).
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