Two color (2+1′) zero kinetic energy pulsed field ionization (ZEKE‐PFI) spectra of I2 ionized via a number of gerade Rydberg excited states have been recorded for the first time. Ionization into both X2Π3/2,g and X2Π1/2,g spin–orbit ionic substates was achieved by selective excitation of Rydberg states having the appropriate spin–orbit ionic core. Adiabatic ionization energies have been determined as 75 069±2 cm−1 for the X2Π 3/2,g state and 80 266±2 cm−1 for the X2Π1/2,g state with ωe values for the two states determined as 240±1 and 229±1 cm−1, respectively. The ZEKE‐PFI spectra recorded for the lower spin–orbit state exhibit non‐Franck–Condon behavior which has been interpreted in terms of an autoionization mechanism. The ZEKE‐PFI technique has also been used to probe the extent of Rydberg and ion‐pair character in a strongly mixed Rydberg/ion‐pair state.

1.
K.
Müller-Dethlefs
,
M.
Sander
, and
E. W.
Schlag
,
Z. Naturforsch, Teil A
39
,
1089
(
1984
).
2.
K.
Müller-Dethlefs
and
E. W.
Schlag
,
Annu. Rev. Phys. Chem.
42
,
109
(
1991
).
3.
R. J.
Donovan
,
R. V.
Flood
,
K. P.
Lawley
,
A. J.
Yencha
, and
T.
Ridley
,
Chem. Phys.
164
,
439
(
1992
).
4.
M. C. R.
Cockett
,
J. G.
Goode
,
R. R. J.
Maier
,
K. P.
Lawley
, and
R. J.
Donovan
,
J. Chem. Phys.
101
,
126
(
1994
).
5.
M. S. N. Al-Kahali, R. J. Donovan, K. P. Lawley, Z. Min, T. Ridley, and P. J. Wilson (unpublished).
6.
See, for example,
A. B.
Cornford
,
D. C.
Frost
,
C. A.
McDowell
,
J. L.
Ragle
, and
I. A.
Stenhouse
,
J. Chem. Phys.
54
,
2651
(
1971
);
A. W.
Potts
and
W. C.
Price
,
Trans. Faraday Soc.
67
,
1242
(
1971
).
7.
B. R.
Higginson
,
D. R.
Lloyd
, and
P. J.
Roberts
,
Chem. Phys. Lett.
19
,
480
(
1973
).
8.
H.
van Lonkhuyzen
and
C. A.
de Lange
,
Chem. Phys.
89
,
313
(
1984
).
9.
A. J.
Yencha
,
M. C. R.
Cockett
,
J. G.
Goode
,
R. J.
Donovan
,
A.
Hopkirk
, and
G.
King
,
Chem. Phys. Lett.
229
,
347
(
1994
).
10.
W. A.
Chupka
,
J. Chem. Phys.
98
,
4520
(
1993
).
11.
R. G.
Tonkyn
,
R. T.
Wiedmann
, and
M. G.
White
,
J. Chem. Phys.
96
,
3696
(
1992
);
R. T.
Wiedmann
,
M. G.
White
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
98
,
7673
(
1993
).,
J. Chem. Phys.
12.
R. D.
Gilbert
and
M. S.
Child
,
Chem. Phys. Lett.
187
,
153
(
1991
).
13.
E.
de Beer
,
W. J.
Buma
, and
C. A.
de Lange
,
J. Chem. Phys.
99
,
3252
(
1994
).
14.
Y.
Xie
,
P. T. A.
Reilly
,
S.
Chilukuri
, and
R. J.
Gordon
,
J. Chem. Phys.
95
,
854
(
1991
).
15.
A.
Mank
,
D.
Rodgers
, and
J. W.
Hepburn
,
Chem. Phys. Lett.
219
,
169
(
1994
).
16.
See
K. P.
Lawley
and
R. J.
Donovan
,
J. Chem. Soc. Faraday II
89
,
1885
(
1993
);
J. C. D.
Brand
and
A. R.
Hoy
,
Appl. Spectrosc. Rev.
23
,
285
(
1987
).
17.
K. P.
Lawley
,
J. Comput. Phys.
70
,
218
(
1987
).
18.
A.
Hiraya
,
K.
Shobatake
,
R. J.
Donovan
, and
A.
Hopkirk
,
J. Chem. Phys.
88
,
52
(
1988
).
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