ZnCH3 and CdCH3 radicals have been prepared in a cold supersonic free jet expansion and their laser‐induced‐fluorescence spectrum recorded for the Ã 2EX̃ 2A1 electronic transition. These spectra show well resolved rotational and spin structure, which has been completely analyzed. This analysis yields the rotational constants and the components of the spin–rotation tensors in the à and X̃ states of both radicals. The observed constants are discussed in terms of the electronic structure of the radicals. It is demonstrated that the upper F2 spin–orbit component of the Ã 2E state of CdCH3 is strongly perturbed by another, dissociative electronic state. This leads to some predissociation of the Ã 2E3/2 component and a broadening of its lines. The rotational and fine structure in this state is also quite perturbed leading to an unusual, but still interpretable spectrum.

1.
R. L.
Jackson
,
J. Chem. Phys.
96
,
5938
(
1992
), and references therein.
2.
J. Haigh and M. R. Aylett, in Laser Microfabrication, edited by D. J. Ehrlich and J. Y. Tsao (Academic, New York, 1989), pp. 453–501.
3.
C.
Jonah
,
P.
Chandra
, and
R.
Bersohn
,
J. Chem. Phys.
55
,
1903
(
1971
).
4.
R. L.
Jackson
,
J. Chem. Phys.
92
,
807
(
1989
).
5.
P. J.
Young
,
R. K.
Gosavi
,
J.
Connor
,
O. P.
Strausz
, and
H. E.
Gunning
,
J. Chem. Phys.
58
,
5280
(
1973
).
6.
A.
Penner
,
A.
Amirav
, and
R.
Bersohn
,
Chem. Phys. Lett.
176
,
147
(
1991
).
7.
E. S. J.
Robles
,
A. M.
Ellis
, and
T. A.
Miller
,
Chem. Phys. Lett.
178
,
185
(
1991
).
8.
A. M.
Ellis
,
E. S. J.
Robles
, and
T. A.
Miller
,
Chem. Phys. Lett.
190
,
599
(
1992
).
9.
C. R.
Brazier
and
P. F.
Bernath
,
J. Chem. Phys.
91
,
4548
(
1989
).
10.
L.
Yu
,
D. W.
Cullin
,
J. M.
Williamson
, and
T. A.
Miller
,
J. Chem. Phys.
98
,
2682
(
1993
), and references therein.
11.
A. M.
Ellis
,
E. S. J.
Robles
, and
T. A.
Miller
,
J. Phys. Chem.
97
,
5809
(
1993
).
12.
D. W.
Cullin
,
L.
Yu
,
J. M.
Williamson
,
M. S.
Platz
, and
T. A.
Miller
,
J. Phys. Chem.
94
,
3387
(
1991
).
13.
J. Cariou and P. Luc, Atlas du Spectre d’Absorption de la Molecule de Tellure (Laboratoire Aime-Cotton, Orsay, France, 1980).
14.
For example, see
R. L.
Jackson
,
Chem. Phys. Lett.
174
,
53
(
1990
), and references therein.
15.
Y.
Endo
,
S.
Saito
, and
E.
Hirota
,
J. Chem. Phys.
81
,
122
(
1984
).
16.
E. Hirota, High-Resolution Spectroscopy of Transient Molecules (Springer, Berlin, 1985).
17.
J. T.
Hougen
,
J. Mol. Spectrosc.
81
,
73
(
1980
).
18.
X. M.
Liu
,
C. P.
Damo
,
T. D.
Lin
,
S. C.
Foster
,
P.
Misra
,
L.
Yu
, and
T. A.
Miller
,
J. Phys. Chem.
93
,
2266
(
1989
).
19.
X. M. Liu, Ph.D. thesis, The Ohio State University, 1990.
20.
R. N. Zare, Angular Momentum (Wiley-Interscience, New York, 1988).
21.
See AIP document no. PAPS JCPSA-99-9376-11 for 11 pages of tables of transition frequencies.
Order by PAPS number and journal reference from American Institute of Physics, Physics Auxiliary Publication Service, 500 Sunnyside Boulevard, Woodbury, New York 11797-2999. The price is $1.50 for each microfiche (60 pages) or $5.00 for photocopies of up to 30 pages, and $0.15 for each additional page over 30 pages. Airmail additional. Make checks payable to the American Institute of Physics.
22.
C.
Jamorski
and
A.
Dargelos
,
Chem. Phys.
164
,
191
(
1992
).
23.
G. Gawboy and I. Shavitt (private communication).
24.
X. Q. Tan, T. M. Cerny, J. M. Williamson, and T. A. Miller (to be published).
25.
Y-C.
Hsu
,
X.
Liu
, and
T. A.
Miller
,
J. Chem. Phys.
90
,
6852
(
1989
).
26.
K. S.
Rao
,
B. P.
Stoicheff
, and
R.
Turner
,
Can. J. Phys.
38
,
1516
(
1960
).
27.
R. L.
Jackson
,
Chem. Phys. Lett.
163
,
315
(
1989
).
28.
A. M. W.
Bakke
,
J. Mol. Spectrosc.
41
,
1
(
1972
), and references therein.
29.
G. Herzberg, Molecular Spectra and Molecular Structure, III. Electronic Spectra and Electronic Structure of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1966).
30.
X.
Liu
,
S. C.
Foster
,
J. M.
Williamson
,
L.
Yu
, and
T. A.
Miller
,
Mol. Phys.
69
,
357
(
1990
).
31.
R-D.
Urban
,
U. M. H.
Birk
, and
H.
Jones
,
J. Chem. Phys.
92
,
14
(
1989
).
32.
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979), p. 679.
33.
M. S.
Child
and
H. C.
Longuet-Higgins
,
Philos. Trans. R. Soc. London, Ser. A
254
,
33
(
1961
).
34.
Y.
Endo
,
S.
Saito
, and
E.
Hirota
,
J. Chem. Phys.
85
,
1770
(
1986
).
This content is only available via PDF.

Supplementary Material

You do not currently have access to this content.