The outer- and inner-valence ionization spectra of the Group VI hydrides H2O,H2S and H2Se below the double-ionization threshold were studied by the SAC-CI (symmetry-adapted-cluster configuration-interaction) general-R method. The SAC-CI method quite accurately reproduced the experimental spectra of these hydrides and gave detailed characterizations of the shake-up states. Several unknown satellite peaks were predicted. The shake-up state which includes excitations to the Rydberg orbitals was found to be very important for describing the satellite peaks of these hydrides. A detailed inner-valence satellite spectrum of H2Se is theoretically proposed prior to any experimental observation.

1.
A. W.
Potts
and
W. C.
Prince
,
Proc. R. Soc. London, Ser. A
326
,
181
(
1972
).
2.
M. Y.
Adam
,
C.
Cauletti
, and
M. N.
Plancastelli
,
J. Electron Spectrosc. Relat. Phenom.
42
,
1
(
1987
).
3.
P.
Baltzer
,
L.
Karlsson
,
M.
Lundqvist
,
B.
Wannberg
,
D. M. P.
Holland
, and
M. A.
MacDonald
,
Chem. Phys.
195
,
403
(
1995
).
4.
P.
Morin
,
M. Y.
Adam
,
I.
Nenner
,
J.
Delwiche
,
M. J.
Hubin-Franskin
, and
P.
Lablanguie
,
Nucl. Instrum. Methods
208
,
77
(
1983
).
5.
M. Y.
Adam
,
A. Naves
de Brito
,
M. P.
Keane
,
S.
Svensson
,
L.
Karlsson
,
E.
Källine
, and
N.
Correia
,
J. Electron Spectrosc. Relat. Phenom.
56
,
241
(
1991
).
6.
K. H.
Tan
,
C. E.
Brion
,
Ph.E.
Van Der Leeuw
, and
M. J.
Van Der Wiel
,
Chem. Phys.
29
,
299
(
1978
).
7.
A. O.
Bawagan
,
L. Y.
Lee
,
K. T.
Leung
, and
C. E.
Brion
,
Chem. Phys.
99
,
367
(
1985
).
8.
A. O.
Bawagan
,
C. E.
Brion
,
E. R.
Davidson
, and
D.
Feller
,
Chem. Phys.
113
,
19
(
1987
).
9.
J. P. D.
Cook
,
C. E.
Brion
, and
A.
Hammet
,
Chem. Phys.
45
,
241
(
1980
).
10.
C. L.
French
,
C. E.
Brion
, and
E. R.
Davidson
,
Chem. Phys.
122
,
247
(
1988
).
11.
C. K.
Subramaniam
,
M. A.
Coplan
,
J. A.
Tossell
,
J. H.
Moore
, and
K. T.
Leung
,
Chem. Phys.
185
,
237
(
1994
).
12.
H.
Nakatsuji
and
T.
Yonezawa
,
Chem. Phys. Lett.
87
,
426
(
1982
).
13.
H.
Wasada
and
K.
Hirao
,
Chem. Phys.
138
,
277
(
1989
).
14.
W.
von Niessen
,
L. S.
Cederbaum
,
J.
Schirmer
,
G.
Diercksen
, and
W. P.
Kraemer
,
J. Electron Spectrosc. Relat. Phenom.
28
,
45
(
1982
).
15.
W.
von Niessen
and
P.
Tomasello
,
Phys. Scr.
41
,
841
(
1990
).
16.
M.
Brosolo
,
P.
Decleva
,
G.
Fronzoni
, and
A.
Lisini
,
J. Mol. Struct.: THEOCHEM
262
,
233
(
1992
);
A.
Lisini
,
M.
Brosolo
,
P.
Decleva
, and
G.
Fronzoni
,
J. Mol. Struct.: THEOCHEM
253
,
333
(
1992
);
G.
Fronzoni
,
G.
De Alti
,
P.
Decleva
, and
A.
Lisini
,
J. Electron Spectrosc. Relat. Phenom.
58
,
375
(
1992
).
17.
H.
Nakatsuji
and
K.
Hirao
,
J. Chem. Phys.
68
,
2053
(
1978
).
18.
H.
Nakatsuji
,
Chem. Phys. Lett.
59
,
362
(
1978
);
H.
Nakatsuji
,
Chem. Phys. Lett.
67
,
329
(
1979
);
H.
Nakatsuji
,
Chem. Phys. Lett.
67
,
334
(
1979
).
19.
H.
Nakatsuji
,
Acta Chim. Acad. Sci. Hung.
129
,
719
(
1992
);
Computational Chemistry—Review of current trends (World Scientific, Singapore, 1997), Vol. 2, pp. 62–124.
20.
H.
Nakatsuji
and
K.
Hirao
,
Chem. Phys. Lett.
79
,
292
(
1981
).
21.
H.
Nakatsuji
,
Chem. Phys.
75
,
425
(
1983
).
22.
H.
Nakatsuji
,
O.
Kitao
, and
T.
Yonezawa
,
J. Chem. Phys.
83
,
723
(
1985
).
23.
H.
Nakatsuji
and
S.
Saito
,
J. Chem. Phys.
91
,
6205
(
1989
);
H.
Nakatsuji
,
M.
Ehara
,
M. H.
Palmer
, and
M. F.
Guest
,
J. Chem. Phys.
97
,
2561
(
1992
);
H.
Nakatsuji
and
M.
Ehara
,
J. Chem. Phys.
97
,
2561
(
1992
);
H.
Nakatsuji
and
M.
Ehara
,
J. Chem. Phys.
101
,
7658
(
1994
);
H.
Nakatsuji
,
J.
Hasegawa
, and
M.
Hada
,
J. Chem. Phys.
104
,
2321
(
1996
).
24.
M.
Ehara
,
Y.
Ohtsuka
, and
H.
Nakatsuji
,
Chem. Phys.
104
,
113
(
1998
).
25.
H.
Nakatsuji
,
Chem. Phys. Lett.
177
,
331
(
1991
).
26.
H.
Nakatsuji
,
J. Chem. Phys.
83
,
731
(
1985
);
H.
Nakatsuji
,
J. Chem. Phys.
83
,
5743
(
1985
);
H.
Nakatsuji
,
J. Chem. Phys.
83
,
6716
(
1991
).
27.
M.
Ehara
and
H.
Nakatsuji
,
Chem. Phys. Lett.
282
,
347
(
1998
).
28.
J.
Hasegawa
,
M.
Ehara
, and
H.
Nakatsuji
,
Chem. Phys.
230
,
23
(
1998
).
29.
M.
Ehara
,
P.
Tomasello
,
J.
Hasegawa
, and
H.
Nakatsuji
,
Theor. Chem. Acc.
102
,
161
(
1999
).
30.
M.
Ehara
and
H.
Nakatsuji
,
Spectrochim. Acta, Part A
55
,
487
(
1999
).
31.
G. Herzberg, Molecular Spectra and Electronic Structure of Polyatomic Molecules (Van Nostrand, New York, 1966).
32.
T. H.
Dunning
,Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
);
D. E.
Woon
and
T. H.
Dunning
,Jr.
,
J. Chem. Phys.
100
,
2975
(
1994
);
A. K.
Wilson
,
D. E.
Woon
,
K. A.
Peterson
, and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
110
,
7667
(
1999
).
33.
H. Dunning, Jr. and P. J. Hay, Methods of Electronic Structure Theory, edited by H. F. Schaefer, III (Plenum, New York, 1977).
34.
S.
Süzer
,
S. T.
Lee
, and
D. A.
Shirley
,
Phys. Rev. A
13
,
1842
(
1976
).
35.
R. I.
Martin
and
D. A.
Shirley
,
J. Chem. Phys.
64
,
3685
(
1976
).
36.
GAUSSIAN 98, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle and J. A. Pople (Gaussian, Inc., Pittsburgh, PA, 1998).
37.
H. Nakatsuji, M. Hada, M. Ehara, J. Hasegawa, T. Nakajima, H. Nakai, O. Kitao, and K. Toyota, “SAC/SAC-CI program system (SAC-CI96) for calculating ground, excited, ionized, and electron-attached states having singlet to septet spin multiplicities,” Kyoto University, 1996.
38.
A.
Cesar
,
H.
Ågren
,
A. Naves
de Brito
,
S.
Svensson
,
L.
Karlsson
,
M. P.
Keane
,
B.
Wannberg
,
P.
Baltzer
,
P. G.
Fournier
, and
J.
Fournier
,
J. Chem. Phys.
93
,
918
(
1990
).
39.
D. M.
Chipman
,
J. Electron Spectrosc. Relat. Phenom.
14
,
323
(
1987
).
40.
M. Y.
Adam
,
P.
Morin
,
C.
Cauletti
, and
M. N.
Plancastelli
,
J. Electron Spectrosc. Relat. Phenom.
36
,
377
(
1985
).
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