Vibrational spectra in the ground electronic states, X̃ 2B1, of fluoro-, chloro-, bromo-, and iodobenzene cations and in the excited electronic states, B̃ 2B2, of chloro- and bromobenzene cations have been measured by mass-analyzed threshold ionization (MATI) via one-photon excitation with vacuum ultraviolet light. The spectra consist mostly of strong 0–0 bands and fundamentals, overtones, and combinations of totally symmetric a1 modes. In particular, the observed vibrational bands in the states have been assigned by referring to the assignments for the ionic ground states and those for the neutral molecules. From the MATI spectra, the ionization energies of fluoro-, chloro-, bromo-, and iodobenzene to the ionic ground states have been determined to be 74 229±5,73 177±5,72 570±5, and 70 638±5 cm−1, respectively. The ionization energies to the states have also been determined to be 91 404±5 and 85 822±5 cm−1 for chloro- and bromobenzene, respectively.

1.
A. Carrington, in Molecular Ions: Geometric and Electronic Structures, edited by J. Berkowitz and K. Groeneveld (Plenum, New York, 1983).
2.
A. Carrington and T. P. Softley, in Molecular Ions: Spectroscopy, Structure, and Chemistry, edited by T. A. Miller and V. E. Bondybey (North–Holland, New York, 1983).
3.
J. P. Maier, in Kinetics of Ion–Molecule Reactions, edited by P. Ausloos (Plenum, New York, 1979).
4.
K. Kimura, S. Katsumata, Y. Achiba, T. Yamazaki, and S. Iwata, Handbook of HeI Photoelectron Spectra of Fundamental Organic Molecules (Japan Scientific Societies, Tokyo, 1981).
5.
A. W.
Potts
,
D.
Edvardsson
,
L.
Karlsson
,
D. M. P.
Holland
,
M. A.
MacDonald
,
M. A.
Hayes
,
R.
Maripuu
,
K.
Siegbahn
, and
W.
von Niessen
,
Chem. Phys.
254
,
385
(
2000
).
6.
D. M. P.
Holland
,
D.
Edvardsson
,
L.
Karlsson
,
R.
Maripuu
,
K.
Siegbahn
,
A. W.
Potts
, and
W.
von Niessen
,
Chem. Phys.
252
,
257
(
2000
).
7.
D. M. P.
Holland
,
D.
Edvardsson
,
L.
Karlsson
,
R.
Maripuu
,
K.
Siegbahn
,
A. W.
Potts
, and
W.
von Niessen
,
Chem. Phys.
253
,
133
(
2000
).
8.
K.
Walter
,
K.
Scherm
, and
U.
Boesl
,
Chem. Phys. Lett.
161
,
473
(
1989
).
9.
K.
Walter
,
K.
Scherm
, and
U.
Boesl
,
J. Phys. Chem.
95
,
1188
(
1991
).
10.
K.
Müller-Dethlefs
,
M.
Sander
, and
E. W.
Schlag
,
Chem. Phys. Lett.
112
,
291
(
1984
).
11.
K.
Müller-Dethlefs
and
E. W.
Schlag
,
Annu. Rev. Phys. Chem.
42
,
109
(
1991
).
12.
I.
Fischer
,
R.
Lindner
, and
K.
Müller-Dethlefs
,
J. Chem. Soc., Faraday Trans.
90
,
2425
(
1994
).
13.
J. W.
Hepburn
,
Chem. Soc. Rev.
25
,
281
(
1996
).
14.
L.
Zhu
and
P.
Johnson
,
J. Chem. Phys.
94
,
5769
(
1991
).
15.
H.
Krause
and
H. J.
Neusser
,
J. Chem. Phys.
97
,
5923
(
1992
).
16.
H.
Krause
and
H. J.
Neusser
,
J. Chem. Phys.
99
,
6278
(
1993
).
17.
W. G.
Scherzer
,
H. L.
Selzle
, and
E. W.
Schlag
,
Phys. Rev. Lett.
72
,
1435
(
1994
).
18.
S. T.
Park
,
S. K.
Kim
, and
M. S.
Kim
,
J. Chem. Phys.
114
,
5568
(
2001
).
19.
S. T.
Park
,
S. K.
Kim
, and
M. S.
Kim
,
Nature (London)
415
,
306
(
2002
).
20.
G.
Lembach
and
B.
Brutschy
,
Chem. Phys. Lett.
273
,
421
(
1997
).
21.
T. G.
Wright
,
S. I.
Panov
, and
T. A.
Miller
,
J. Chem. Phys.
102
,
4793
(
1995
).
22.
H.
Shinohara
,
S.
Sato
, and
K.
Kimura
,
J. Phys. Chem. A
101
,
6736
(
1997
).
23.
G.
Lembach
and
B.
Brutschy
,
J. Phys. Chem.
100
,
19758
(
1996
).
24.
Th. L.
Grebner
and
H. J.
Neusser
,
Int. J. Mass Spectrom. Ion Processes
159
,
137
(
1996
).
25.
X.
Ripoche
,
I.
Dimicoli
,
J.
LeCalve
,
F.
Piuzzi
, and
R.
Botter
,
Chem. Phys.
124
,
305
(
1988
).
26.
K.
Walter
,
U.
Boesl
, and
E. W.
Schlag
,
Chem. Phys. Lett.
162
,
261
(
1989
).
27.
J. G.
Goode
,
J. D.
Hofstein
, and
P. M.
Johnson
,
J. Chem. Phys.
107
,
1703
(
1997
).
28.
R.
Anand
,
J. D.
Hofstein
,
J. E.
LeClaire
, and
P. M.
Johnson
,
J. Phys. Chem. A
103
,
8927
(
1999
).
29.
R.
Hilbig
and
R.
Wallenstein
,
IEEE J. Quantum Electron.
QE-19
,
1759
(
1983
).
30.
E. B.
Wilson
, Jr.
,
Phys. Rev.
45
,
706
(
1934
).
31.
T.
Baer
,
B. P.
Tsai
,
D.
Smith
, and
P. T.
Murray
,
J. Chem. Phys.
64
,
2460
(
1976
).
32.
G. Varsanyi, Assignments for Vibrational Spectra of Seven Hundred Benzene Derivatives (Adams Hilger, London, 1974).
33.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 98, Revision A.6 Gaussian, Inc., Pittsburgh, Pennsylvania, 1998.
34.
Y. Y. Youn, C. H. Kwon, J. C. Choe, and M. S. Kim (unpublished).
35.
(a)
W.
Kong
,
D.
Rodgers
, and
J. W.
Hepburn
,
J. Chem. Phys.
99
,
8571
(
1993
);
(b)
A.
Mank
,
T.
Nguyen
,
J. D. D.
Martin
, and
J. W.
Hepburn
,
Phys. Rev. A
51
,
R1
(
1995
);
(c)
J. W.
Hepburn
,
J. Chem. Phys.
107
,
7106
(
1997
).
36.
(a)
F.
Merkt
and
T. P.
Softley
,
J. Chem. Phys.
96
,
4149
(
1992
);
(b)
R.
Signorell
and
F.
Merkt
,
J. Chem. Phys.
109
,
9762
(
1998
).
This content is only available via PDF.
You do not currently have access to this content.