The collisionally induced absorption process and the broadening of the 6P resonance line of the Cs–Rg system (Rg=Xe, Kr, Ar, and Ne) are studied theoretically by the symmetry adapted cluster‐configuration interaction (SAC‐CI) method. The potential energy curves and the transition moments of the CsRg system correlating to the 6S, 6P, 5D, and 7S states of the Cs atom are investigated. The reduced absorption coefficients are calculated using the quasistatic approximation and the results agree well with the experimental data. The monotonic dependence of the spectral peaks on the rare gas species is due to the similar monotonic dependence of the avoided crossing point between the 7sΣ and 5dΣ states. The absorption intensities decrease as the rare gas atom is substituted from Xe to Ne in agreement with the experimental observation. The intensities of the 6sΣ–5dΣ transitions are calculated to be larger than those of the 6sΣ–7sΣ ones, since the former transitions are induced at larger internuclear distances than the latter.

1.
P. R.
Brooks
,
Chem. Rev.
88
,
407
(
1988
).
2.
G.
Moe
,
A. C.
Tam
, and
W.
Happer
,
Phy. Rev. A
14
,
349
(
1976
).
3.
A. C.
Tam
,
G.
Moe
,
B. R.
Bulos
, and
W.
Happer
,
Opt. Commun.
16
,
376
(
1976
).
4.
A. C.
Tam
,
G.
Moe
,
W.
Park
, and
W.
Happer
,
Phys. Rev. Lett.
35
,
85
(
1975
).
5.
R. E.
Hedges
,
D. L.
Drummond
, and
Alan
Gallagher
,
Phys. Rev. A
6
,
1519
(
1972
).
6.
J. F.
Kielkopf
and
N. F.
Allard
,
J. Phys. B
13
,
709
(
1980
);
J. F.
Kielkopf
and
N. F.
Allard
,
Rev. Mod. Phys.
54
,
1103
(
1982
).
7.
W. E.
Baylis
,
J. Chem. Phys.
51
,
2665
(
1969
).
8.
J.
Pascale
and
J.
Vandeplanque
,
J. Chem. Phys.
60
,
2278
(
1974
).
9.
J.
Pascale
,
J. Chem. Phys.
67
,
204
(
1977
).
10.
B.
Sayer
,
J. P.
Visticot
, and
J.
Pascale
,
J. Phys. (Paris)
39
,
361
(
1978
).
11.
H.
Nakatsuji
and
M.
Ehara
,
Chem. Phys. Lett.
172
,
261
(
1990
).
12.
P. D.
Kleiber
and
K. M.
Sando
,
Phys. Rev. A
35
,
3175
(
1987
).
13.
P. D.
Kleiber
,
A. K.
Fletcher
, and
K. M.
Sando
,
Phys. Rev. A
37
,
3584
(
1988
).
14.
K.
Ueda
,
T.
Komatsu
, and
Y.
Sato
,
J. Chem. Phys.
91
,
4495
,
4499
(
1989
);
K.
Ueda
,
H.
Sotome
, and
Y.
Sato
,
J. Chem. Phys.
94
,
1903
,
1907
(
1991
); ,
J. Chem. Phys.
K.
Ueda
,
O.
Sonobe
,
H.
Chiba
, and
Y.
Sato
,
J. Chem. Phys.
95
,
8083
(
1991
); ,
J. Chem. Phys.
T.
Maeyama
,
H.
Ito
,
H.
Chiba
,
K.
Ohmori
,
K.
Ueda
, and
Y.
Sato
,
J. Chem. Phys.
97
,
9492
(
1992
).,
J. Chem. Phys.
15.
K.
Ohmori
,
T.
Kurosawa
,
H.
Chiba
,
M.
Okunishi
, and
Y.
Sato
,
J. Chem. Phys.
100
,
5381
(
1994
).
16.
H.
Nakatsuji
and
K.
Hirao
,
J. Chem. Phys.
68
,
2053
(
1978
).
17.
H.
Nakatsuji
,
Chem. Phys. Lett.
59
,
362
(
1978
);
H.
Nakatsuji
,
67
,
329
,
334
(
1979
).,
Chem. Phys. Lett.
18.
H.
Nakatsuji
,
Acta Chim. Hungarica
129
,
719
(
1992
).
19.
H.
Nakatsuji
,
J.
Ushio
, and
T.
Yonezawa
,
Can. J. Chem.
63
,
1857
(
1985
).
20.
Y.
Mizukami
and
H.
Nakatsuji
,
J. Chem. Phys.
92
,
6084
(
1990
).
21.
J.
Holmtzmark
,
Ann. Phys. (Leipzig)
58
,
577
(
1919
).
22.
A.
Jablonski
,
Phys. Rev.
68
,
78
(
1945
).
23.
S. Y.
Chen
and
M.
Takeo
,
Rev. Mod. Phys.
29
,
20
(
1957
).
24.
W. R.
Wadt
and
P. J.
Hay
,
J. Chem. Phys.
82
,
284
(
1985
).
25.
S. R.
Langhoff
,
C. W.
Bauschlicher
, and
H.
Partrige
,
J. Phys. B
18
,
13
(
1985
).
26.
S. Huzinaga, J. Andzelm, M. Klobukowski, E. Radzio-Andzelm, Y. Sakai, and H. Tatewaki, Gaussian Basis Sets for Molecular Calculations (Elsevier, Amsterdam, 1984).
27.
W. C.
Ermler
,
Y. S.
Lee
,
K. S.
Pitzer
, and
N. W.
Winter
,
J. Chem. Phys.
69
,
716
(
1971
).
28.
H.
Nakatsuji
,
Chem. Phys.
75
,
425
(
1983
).
29.
M. Dupuis, J. D. Watts, H. O. Viller, and G. J. B. Hurst, Program System HONDO7, Program Library No. 544, Computer Center of the Institute for Molecular Science, 1989.
30.
H. Nakatsuji, Program system for SAC and SAC-CI calculations, Program Library No. 146 (Y4/SAC), Data Processing Center of Kyoto University, 1985;
H. Nakatsuji, Program Library SAC85 (No. 1396), Computer Center of the Institute for Molecular Science, Okazaki, Japan, 1986.
31.
(a)
H.
Nakatsuji
,
Y.
Matsuzaki
, and
T.
Yonezawa
,
J. Chem. Phys.
88
,
5759
(
1988
);
(b)
C. A.
Masmanidis
,
H. H.
Jaffe
, and
R. L.
Ellis
,
J. Phys. Chem.
79
,
2052
(
1975
);
(c)
S.
Kato
,
R. L.
Jaffe
,
A.
Komornicki
, and
K.
Morokuma
,
J. Chem. Phys.
78
,
4567
(
1983
).
32.
C. E. Moore, Atomic Energy Levels (National Bureau of Standards, Washington, D. C, 1971), Vol. 2.
33.
G.
Alber
and
J.
Cooper
,
Phys. Rev. A
33
,
3084
(
1986
).
34.
U.
Buck
and
H.
Pauly
,
Z. Phys.
208
,
390
(
1968
).
35.
Q.
Ma
and
R. H.
Tipping
,
J. Chem. Phys.
95
,
6290
(
1991
);
Q.
Ma
and
R. H.
Tipping
,
96
,
8655
(
1992
); ,
J. Chem. Phys.
Q.
Ma
and
R. H.
Tipping
,
97
,
818
(
1992
); ,
J. Chem. Phys.
Q.
Ma
and
R. H.
Tipping
,
100
,
2537
(
1994
).,
J. Chem. Phys.
This content is only available via PDF.
You do not currently have access to this content.