A new analysis is presented of the recent photoionization spectrum of H2O, excited by double resonance via several rotational sublevels of the (100) vibrational level of the C̃(1B1) state. Evidence for a previously unsuspected strong f series indicates significant d orbital contamination of the nominal p orbital in the intermediate state. This is the first report of an f series in the Rydberg state of any asymmetric top. Previous d series analyses of single-photon photoionization spectra terminating on the (100) level of H2O+ are also corrected and extended to a wider range of excited rotational electronic states. The d series appears to contain absent lines, indicative of predissociation. Some lines remain unassigned, but there is no systematic evidence of either s or p series.

1.
P. Andresen and R. Schinke, in Molecular Photodissociation Dynamics, edited by M. N. R. Ashfold and J. E. Baggot (Advances in Gas-Phase Photo-chemistry and Kinetics, Royal Society of Chemistry, London, 1987) Chap. 3.
2.
M. P. Docker, A. Hodgson, and J. P. Simons, in Ref. 1, Chap. 4.
3.
M. N. R.
Ashfold
,
J. M.
Bayley
, and
R. N.
Dixon
,
Can. J. Phys.
62
,
1806
(
1984
).
4.
J. W. C.
Johns
,
Can. J. Phys.
41
,
209
(
1963
).
5.
J. W. C.
Johns
,
Can. J. Phys.
49
,
944
(
1971
).
6.
M. N. R.
Ashfold
,
J. M.
Bayley
, and
R. N.
Dixon
,
Chem. Phys.
84
,
35
(
1984
).
7.
M. S.
Child
,
Philos. Trans. R. Soc. London, Ser. A
355
,
1623
(
1997
).
8.
S.
Bell
,
J. Mol. Spectrosc.
16
,
205
(
1965
).
9.
G.
Theodorakopoulos
,
C. I.
Nicloaides
,
R. J.
Buenker
, and
S. D.
Peyerimhoff
,
Chem. Phys. Lett.
105
,
253
(
1984
).
10.
D. M.
Hirst
and
M. S.
Child
,
Mol. Phys.
77
,
463
(
1992
).
11.
G.
Theodorakopoulos
,
C. I.
Nicloaides
,
R. J.
Buenker
, and
S. D.
Peyer-imhoff
,
Chem. Phys. Lett.
89
,
164
(
1982
).
12.
R. D.
Gilbert
,
M. S.
Child
, and
J. W. C.
Johns
,
Mol. Phys.
74
,
473
(
1991
).
13.
E. H.
Abramson
,
J.
Zhang
, and
D. G.
Imre
,
J. Chem. Phys.
93
,
947
(
1990
).
14.
K.
Watanabe
and
M.
Zelikoff
,
J. Opt. Soc. Am.
43
,
753
(
1953
).
15.
E.
Ishiguro
,
M.
Sasanuma
,
H.
Masuko
,
Y.
Morioka
, and
M.
Nakamura
,
J. Phys. B
11
,
993
(
1978
).
16.
R. H.
Page
,
R. J.
Larkin
,
Y. R.
Shen
, and
Y. T.
Lee
,
J. Chem. Phys.
88
,
2249
(
1988
).
17.
M. J.
Vrakking
,
Y. T.
Lee
,
R. D.
Gilbert
, and
M. S.
Child
,
J. Chem. Phys.
98
,
1902
(
1993
).
18.
M. S.
Child
and
Ch.
Jungen
,
J. Chem. Phys.
93
,
7756
(
1990
).
19.
O.
Dutuit
,
A.
Tabche-Fouhaile
,
I.
Nenner
,
H.
Frohlich
, and
P. M.
Guyon
,
J. Chem. Phys.
83
,
584
(
1985
).
20.
W. L.
Glab
,
J. Chem. Phys.
107
,
5979
(
1997
).
21.
W. L.
Glab
,
M. S.
Child
, and
S. T.
Pratt
,
J. Chem. Phys.
109
,
3062
(
1998
).
22.
E. E.
Mayer
,
H. G.
Hedderich
, and
E. R.
Grant
,
J. Chem. Phys.
108
,
1886
(
1998
).
23.
G.
Hilber
,
A.
Lago
, and
R.
Wallenstein
,
J. Opt. Soc. Am. B
4
,
1753
(
1987
).
24.
C. H.
Greene
and
Ch.
Jungen
,
Adv. At. Mol. Phys.
21
,
51
(
1985
).
25.
P. R. Bunker, Molecular Symmetry and Structure, 2nd ed. (NRC Ottawa, 1999).
26.
R. G.
Tonkyn
,
R.
Weidmann
,
E. R.
Grant
, and
M. G.
White
,
J. Chem. Phys.
95
,
7033
(
1991
).
27.
J. E.
Reutt
,
L. S.
Wang
,
L. S.
Lee
, and
D. A.
Shirley
,
J. Chem. Phys.
85
,
6928
(
1986
).
28.
H.
Lew
,
Can. J. Phys.
54
,
2028
(
1976
).
29.
G.
Theodorakopoulos
,
I. D.
Petsalakis
, and
M. S.
Child
,
J. Phys. B
29
,
4543
(
1996
).
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