We report vibrationally resolved spectra of the S1←S0 transition of chlorobenzene using resonance-enhanced multiphoton ionization spectroscopy. We study chlorobenzene-h5 as well as its perdeuterated isotopologue, chlorobenzene-d5. Changes in the form of the vibrational modes between the isotopologues and also between the S0 and S1 electronic states are discussed for each species. Vibrational bands are assigned utilizing quantum chemical calculations, previous experimental results, and isotopic shifts, including those between the 35Cl and 37Cl isotopologues. Previous work and assignments of the S1 spectra are discussed. Additionally, the vibrations in the ground state cation, D 0 + , are considered, since these have also been used by previous workers in assigning the excited neutral state spectra.

1.
G.
Herzberg
,
Molecular Spectra and Molecular Structure III: Electronic Spectra and Electronic Structure of Polyatomic Molecules
(
Krieger
,
Malabar
,
1991
).
2.
D. H.
Whiffen
,
J. Chem. Soc.
1350
(
1956
).
3.
J. E.
Purvis
,
J. Chem. Soc.
99
,
911
(
1911
).
4.
H.
Sponer
and
S. H.
Wollman
,
J. Chem. Phys.
9
,
816
(
1941
).
5.
T.
Cvitaš
and
J. M.
Hollas
,
Mol. Phys.
18
,
101
(
1970
).
6.
H. D.
Bist
,
V. N.
Sarin
,
A.
Ojha
, and
Y. S.
Jain
,
Appl. Spectrosc.
24
,
292
(
1970
).
7.
H. D.
Bist
,
V. N.
Sarin
,
A.
Ojha
, and
Y. S.
Jain
,
Spectrochim. Acta, Part A
26
,
841
(
1970
).
8.
Y. S.
Jain
and
H. D.
Bist
,
J. Mol. Spectrosc.
47
,
126
(
1973
).
9.
A. M.
Gardner
and
T. G.
Wright
,
J. Chem. Phys.
135
,
114305
(
2011
).
10.
J.-I.
Murakami
,
K.
Kaya
, and
M.
Ito
,
J. Chem. Phys.
72
,
3263
(
1980
).
11.
S. L.
Anderson
,
D. M.
Rider
, and
R. N.
Zare
,
Chem. Phys. Lett.
93
,
11
(
1982
).
12.
K.
Walter
,
K.
Scherm
, and
U.
Boesl
,
J. Phys. Chem.
95
,
1188
(
1991
).
13.
A.
de la Cruz
,
J.
Campos
, and
M.
Ortiz
,
J. Mol. Spectrosc.
180
,
305
(
1996
).
14.
P.
Imhof
and
K.
Kleinermanns
,
Chem. Phys.
270
,
227
(
2001
).
15.
A. M.
Bass
and
H.
Sponer
,
J. Opt. Soc. Am.
40
,
389
(
1950
).
16.
H.
Schüler
and
A.
Woeldike
,
Phys. Z.
42
,
390
(
1941
).
17.
A.
Woeldike
,
Z. Naturforsch.
1
,
566
(
1946
).
18.
H.
Schüler
,
Z. Naturforsch., A
2
,
556
(
1947
).
19.
T. R.
Nanney
,
R. T.
Bailey
, and
E. R.
Lippincott
,
Spectrochim. Acta
21
,
1495
(
1965
).
20.
G.
Varsányi
,
Assignments of the Vibrational Spectra of Seven Hundred Benzene Derivatives
(
Wiley
,
New York
,
1974
).
21.
P.
Asselin
,
A.
Gouzerh
,
F.
Piuzzi
, and
I.
Dimicoli
,
Chem. Phys.
175
,
387
(
1993
).
22.
A. W.
Potts
,
M. L.
Lyus
,
E. P. F.
Lee
, and
G. H.
Fattahallah
,
J. Chem. Soc., Faraday Trans. 2
76
,
556
(
1980
).
23.
X.
Ripoche
,
I.
Dimicoli
,
J.
Le Calvé
,
F.
Piuzzi
, and
R.
Botter
,
Chem. Phys.
124
,
305
(
1988
).
24.
T. G.
Wright
,
S. I.
Panov
, and
T. A.
Miller
,
J. Chem. Phys.
102
,
4793
(
1995
).
25.
C. J.
Kwon
,
H. L.
Kim
, and
M. S.
Kim
,
J. Chem. Phys.
116
,
10361
(
2002
).
26.
G.
Lembach
and
B.
Brutschy
,
Chem. Phys. Lett.
273
,
421
(
1997
).
27.
E. B.
Wilson
, Jr.
,
Phys. Rev.
45
,
706
(
1934
).
28.
P.
Butler
,
D. B.
Moss
,
H.
Yin
,
T. W.
Schmidt
, and
S. H.
Kable
,
J. Chem. Phys.
127
,
094303
(
2007
).
29.
I.
Pugliesi
,
N. M.
Tonge
, and
M. C. R.
Cockett
,
J. Chem. Phys.
129
,
104303
(
2008
).
30.
J. P.
Harris
,
A.
Andrejeva
,
W. D.
Tuttle
,
I.
Pugliesi
,
C.
Schriever
, and
T. G.
Wright
,
J. Chem. Phys.
141
,
244315
(
2014
).
31.
R. S.
Mulliken
,
J. Chem. Phys.
23
,
1997
(
1955
).
32.
G.
Herzberg
,
Molecular Spectra and Molecular Structure II: Infrared and Raman Spectra of Polyatomic Molecules
(
Krieger
,
Malabar
,
1991
), p.
272
.
33.
A. M.
Gardner
,
A. M.
Green
,
V. M.
Tame-Reyes
,
V. H.
Wilton
, and
T. G.
Wright
,
J. Chem. Phys.
138
,
134303
(
2013
).
34.
A. M.
Gardner
,
A. M.
Green
,
V. M.
Tame-Reyes
,
K. L.
Reid
,
J. A.
Davis
,
V. H. K.
Parkes
, and
T. G.
Wright
,
J. Chem. Phys.
140
,
114308
(
2014
).
35.
F.
Duschinsky
,
Acta Physicochim. URSS
7
,
551
(
1937
).
36.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
,
G. E.
Scuseria
,
M. A.
Robb
,
J. R.
Cheeseman
,
G.
Scalmani
,
V.
Barone
,
B.
Mennucci
,
G. A.
Petersson
,
H.
Nakatsuji
,
M.
Caricato
,
X.
Li
,
H. P.
Hratchian
,
A. F.
Izmaylov
,
J.
Bloino
,
G.
Zheng
,
J. L.
Sonnenberg
,
M.
Hada
,
M.
Ehara
,
K.
Toyota
,
R.
Fukuda
,
J.
Hasegawa
,
M.
Ishida
,
T.
Nakajima
,
Y.
Honda
,
O.
Kitao
,
H.
Nakai
,
T.
Vreven
,
J. A.
Montgomery
, Jr.
,
J. E.
Peralta
,
F.
Ogliaro
,
M.
Bearpark
,
J. J.
Heyd
,
E.
Brothers
,
K. N.
Kudin
,
V. N.
Staroverov
,
R.
Kobayashi
,
J.
Normand
,
K.
Raghavachari
,
A.
Rendell
,
J. C.
Burant
,
S. S.
Iyengar
,
J.
Tomasi
,
M.
Cossi
,
N.
Rega
,
J. M.
Millam
,
M.
Klene
,
J. E.
Knox
,
J. B.
Cross
,
V.
Bakken
,
C.
Adamo
,
J.
Jaramillo
,
R.
Gomperts
,
R. E.
Stratmann
,
O.
Yazyev
,
A. J.
Austin
,
R.
Cammi
,
C.
Pomelli
,
J. W.
Ochterski
,
R. L.
Martin
,
K.
Morokuma
,
V. G.
Zakrzewski
,
G. A.
Voth
,
P.
Salvador
,
J. J.
Dannenberg
,
S.
Dapprich
,
A. D.
Daniels
,
Ö.
Farkas
,
J. B.
Foresman
,
J. V.
Ortiz
,
J.
Cioslowski
, and
D. J.
Fox
, gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT, 2009.
37.
I.
Pugliesi
and
K.
Muller-Dethlefs
,
J. Phys. Chem. A
110
,
4657
(
2006
), a free download of the software can be found at http://www.fclab2.net10.1021/jp058226h.
38.
PGOPHER, a Program for Simulating Rotational, Vibrational and Electronic Structure, C. M. Western, University of Bristol, http://pgopher.chm.bris.ac.uk. PGOPHER version 8.0, C M Western, 2014, University of Bristol Research Data Repository, doi:10.5523/bris.huflggvpcuc1zvliqed497r2.
39.
See supplementary material at http://dx.doi.org/10.1063/1.4929996 for tables of assignments of the 37ClBz-h5 and 37ClBz-d5 spectra, as well as the derived fundamental wavenumbers.
40.
U.
Boesl
,
R.
Zimmermann
,
C.
Weickhardt
,
D.
Lenoir
,
K.-W.
Schramm
,
A.
Kettrup
, and
E. W
Schlag
,
Chemosphere
29
,
1429
(
1994
).
41.
R.
Vasudev
and
J. C. D.
Brand
,
J. Mol. Spectrosc.
75
,
288
(
1979
).
42.
Y.-J.
Liu
,
P.
Persson
, and
S.
Lunell
,
J. Phys. Chem. A
108
,
2339
(
2004
).
43.
T.
Deguchi
,
N.
Takeyasu
, and
T.
Imasaka
,
Appl. Spectrosc.
56
,
1241
(
2002
).
44.
Y.-Z.
Liu
,
C.-C.
Qin
,
S.
Zhang
,
Y.-M.
Wang
, and
B.
Zhang
,
Acta Phys.-Chim. Sin.
27
,
965
(
2011
).
45.
T. G.
Dietz
,
M. A.
Duncan
,
M. G.
Liverman
, and
R. E.
Smalley
,
J. Chem. Phys.
73
,
4816
(
1980
).
46.
J. R.
Gascooke
,
U. N.
Alexander
, and
W. D.
Lawrance
,
J. Chem. Phys.
134
,
184301
(
2011
).

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