The line intensity of photoelectron spectra when either the neutral or cationic species display a Renner-Teller coupling is derived and applied to the modeling of the photoelectron spectra of CNC, CCN, and HCCN. The rovibronic energy levels of these three radicals and of their cations are investigated starting from ab initio results. A model treating simultaneously the bending mode and the overall rotation is developed to deal with the quasilinearity problem in CNC+, CCN+, and HCCN and accounts for the large amplitude nature of their bending mode. This model is extended to treat the Renner-Teller coupling in CNC, CCN, and HCCN+. Based on the derived photoelectron line intensity, the photoelectron spectra of all three molecules are calculated and compared to the experimental ones.
REFERENCES
1.
S.
Willitsch
, U.
Hollenstein
, and F.
Merkt
, J. Chem. Phys.
120
, 1761
(2004
).2.
R.
Signorell
and F.
Merkt
, Faraday Discuss.
115
, 205
(2000
).3.
S. T.
Pratt
, P. M.
Dehmer
, and J. L.
Dehmer
, J. Chem. Phys.
95
, 6238
(1991
).4.
S. T.
Pratt
, P. M.
Dehmer
, and J. L.
Dehmer
, J. Chem. Phys.
99
, 6233
(1993
).5.
A. N.
Petelin
and A. A.
Kiselev
, Int. J. Quantum Chem.
6
, 701
(1972
).6.
G. A.
Garcia
, J.
Krüger
, B.
Gans
, C.
Falvo
, L. H.
Coudert
, and J.-C.
Loison
, J. Chem. Phys.
147
, 013908
(2017
).7.
A. D.
Buckingham
, B. J.
Orr
, and J. M.
Sichel
, Philos. Trans. R. Soc., A
268
, 147
(1970
).8.
J.
Xie
and R. N.
Zare
, J. Chem. Phys.
93
, 3033
(1990
).9.
J.
Xie
and R. N.
Zare
, J. Chem. Phys.
97
, 2891
(1992
).10.
F.
Merkt
and T. P.
Softley
, Int. Rev. Phys. Chem.
12
, 205
(1993
).11.
M. S.
Child
and C.
Jungen
, J. Chem. Phys.
93
, 7756
(1990
).12.
K.
Müller-Dethlefs
, J. Chem. Phys.
95
, 4821
(1991
).13.
R.
Signorell
and F.
Merkt
, Mol. Phys.
92
, 793
(1997
).14.
S.
Willitsch
, J. M.
Dyke
, and F.
Merkt
, Mol. Phys.
102
, 1543
(2004
).15.
S.
Willitsch
and F.
Merkt
, Int. J. Mass Spectrom.
245
, 14
(2005
).16.
L. H.
Coudert
, J. Mol. Spectrosc.
154
, 427
(1992
).17.
L. H.
Coudert
, J. Mol. Spectrosc.
165
, 406
(1994
).18.
L. H.
Coudert
, J. Mol. Spectrosc.
181
, 246
(1997
).19.
R.
Lanquetin
, L. H.
Coudert
, and C.
Camy-Peyret
, J. Mol. Spectrosc.
195
, 54
(1999
).20.
L. H.
Coudert
, Mol. Phys.
96
, 941
(1999
).21.
L. H.
Coudert
, J. Mol. Spectrosc.
330
, 112
(2016
).22.
C.
Jungen
and A. J.
Merer
, Mol. Phys.
40
, 1
(1980
).23.
S.
Carter
and N. C.
Handy
, Mol. Phys.
52
, 1367
(1984
).24.
M.
Perić
, S. D.
Peyerimhoff
, and R. J.
Buenker
, Int. Rev. Phys. Chem.
4
, 85
(1985
).25.
A.
Alijah
and G.
Duxbury
, J. Mol. Spectrosc.
211
, 7
(2002
).26.
J. G.
Hill
, A.
Mitrushchenkov
, K. E.
Yousaf
, and K. A.
Peterson
, J. Chem. Phys.
135
, 144309
(2011
).27.
A. O.
Mitrushchenkov
, J. Chem. Phys.
136
, 024108
(2012
).28.
H.
Partridge
and D. W.
Schwenke
, J. Chem. Phys.
106
, 4618
(1997
).29.
S.
Wu
, Y.
Chen
, X.
Yang
, Y.
Guo
, Y.
Liu
, Y.
Li
, R. J.
Buenker
, and P.
Jensen
, J. Mol. Spectrosc.
225
, 96
(2004
).30.
S. Y.
Truong
, A. J.
Yencha
, A. M.
Juarez
, S. J.
Cavanagh
, P.
Bolognesi
, and G. C.
King
, Chem. Phys.
355
, 183
(2009
).31.
M. S.
Ford
, K.
Müller-Dethlefs
, M.
Kitajima
, H.
Tanaka
, Y.
Tamenori
, A.
De Fanis
, and K.
Ueda
, J. Phys. Chem. A
114
, 11133
(2010
).32.
J.
Koput
, J. Phys. Chem. A
106
, 6183
(2002
).33.
F.
Brown
, S.
Saito
, and S.
Yamamoto
, J. Mol. Spectrosc.
143
, 203
(1990
).34.
A. J.
Merer
and D. N.
Travis
, Can. J. Phys.
44
, 353
(1966
).35.
Pd.
Rajendra
and P.
Chandra
, J. Chem. Phys.
114
, 1589
(2001
).36.
P.
Jensen
and W. P.
Kraemer
, J. Mol. Spectrosc.
129
, 216
(1988
).37.
M.
Wyss
, E.
Riaplov
, J. P.
Maier
, M.
Hochlaf
, and P.
Rosmus
, Helv. Chim. Acta
84
, 1432
(2001
).38.
A. J.
Merer
and D. N.
Travis
, Can. J. Phys.
43
, 1795
(1965
).39.
Z.-X.
Zhao
, H.-X.
Zhang
, and C.-C.
Sun
, J. Phys. Chem. A
112
, 12125
(2008
).40.
N.
Inostroza
, X.
Huang
, and T. J.
Lee
, J. Chem. Phys.
135
, 244310
(2011
).41.
H.
Kohguchi
, Y.
Ohshima
, and Y.
Endo
, J. Chem. Phys.
106
, 5429
(1997
).42.
M. C.
McCarthy
, C. A.
Gottlieb
, A. L.
Cooksy
, and P.
Thaddeus
, J. Chem. Phys.
103
, 7779
(1995
).43.
C.
Camy-Peyret
and J.-M.
Flaud
, Mol. Phys.
32
, 523
(1976
).44.
J. T.
Hougen
, P. R.
Bunker
, and J. W. C.
Johns
, J. Mol. Spectrosc.
34
, 136
(1970
).45.
M. A.
Mekhtiev
, P. D.
Godfrey
, and V.
Szalay
, J. Mol. Spectrosc.
180
, 42
(1996
).46.
M.
Abramowitz
and I. A.
Stegun
, Handbook of Mathematical Functions with Formulas, Graphs, and Mathematical Tables
, National Bureau of Standards Applied Mathematics Series Vol. 55 (For sale by the Superintendent of Documents, U.S. Government Printing Office
, Washington, DC
, 1964
), pp. xiv+1046
.47.
48.
P. R.
Bunker
, Molecular Symmetry and Spectroscopy
, 1st ed. (Academic Press
, New York
, 1979
).49.
C.
Jungen
, K.-E. J.
Hallin
, and A. J.
Merer
, Mol. Phys.
40
, 25
(1980
).50.
P. R.
Bunker
and J. M. R.
Stone
, J. Mol. Spectrosc.
41
, 310
(1972
).51.
G.
Duxbury
, B. D.
McDonald
, M. V.
Gogh
, A.
Alijah
, C.
Jungen
, and H.
Palivan
, J. Chem. Phys.
108
, 2336
(1998
).52.
P.
Jensen
, T. E.
Odaka
, W. P.
Kraemer
, T.
Hirano
, and P. R.
Bunker
, Spectrochim. Acta, Part A
58
, 763
(2002
).© 2018 Author(s).
2018
Author(s)
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