Excited-state geometries and electronic spectra of butadiene, acrolein, and glyoxal have been investigated by the symmetry adapted cluster configuration interaction (SAC-CI) method in their s-trans conformation. Valence and Rydberg states below the ionization threshold have been precisely calculated with sufficiently flexible basis sets. Vertical and adiabatic excitation energies were well reproduced and the detailed assignments were given taking account of the second moments. The deviations of the vertical excitation energies from the experiment were less than for all cases. The SAC-CI geometry optimization has been applied to some valence and Rydberg excited states of these molecules in the planar structure. The optimized ground- and excited-state geometries agree well with the available experimental values; deviations lie within and 0.7° for the bond lengths and angles, respectively. The force acting on the nuclei caused by the excitations has been discussed in detail by calculating the SAC-CI electron density difference between the ground and excited states; the geometry relaxation was well interpreted with the electrostatic force theory. In Rydberg excitations, geometry changes were also noticed. Doubly excited states (so-called states) were investigated by the SAC-CI general- method considering up to quadruple excitations. The characteristic geometrical changes and large energetic relaxations were predicted for these states.
REFERENCES
1.
A. D.
Walsh
, Trans. Faraday Soc.
41
, 498
(1945
).2.
W. C.
Price
and A. D.
Walsh
, Proc. R. Soc. London, Ser. A
174
, 220
(1940
).3.
A. D.
Walsh
, Trans. Faraday Soc.
19
, 1425
(1945
).4.
W. M.
Flicker
, O. A.
Mosher
, and A.
Kuppermann
, J. Chem. Phys.
59
, 6502
(1973
).5.
W. M.
Flicker
, O. A.
Mosher
, and A.
Kuppermann
, Chem. Phys.
30
, 307
(1978
).6.
7.
8.
R.
McDiarmid
, Chem. Phys. Lett.
34
, 130
(1975
);9.
J. P.
Doering
and R.
McDiarmid
, J. Chem. Phys.
73
, 3617
(1980
).10.
R.
McDiarmid
, Chem. Phys. Lett.
188
, 423
(1992
).11.
R. R.
Chadwick
, D. P.
Gerrity
, and B. S.
Hudson
, Chem. Phys. Lett.
115
, 24
(1985
).12.
R. S.
Becker
, K.
Inuzuka
, and J.
King
, J. Chem. Phys.
52
, 5164
(1970
).13.
M.
Reguero
, M.
Olivucci
, F.
Bernardi
, and M. A.
Robb
, J. Am. Chem. Soc.
116
, 2103
(1994
);K. W.
Paulisse
, T. O.
Friday
, M. L.
Graske
, and W. P.
Polik
, J. Chem. Phys.
113
, 184
(2000
);M.
Olivucci
, F.
Bernardi
, I. N.
Ragazos
, and M. A.
Robb
, J. Am. Chem. Soc.
115
, 3710
(1993
).14.
15.
16.
O.
Kitao
and H.
Nakatsuji
, Chem. Phys. Lett.
143
, 528
(1988
).17.
S.
Shih
, R. J.
Buenker
, and S. D.
Peyerimhoff
, Chem. Phys. Lett.
16
, 244
(1972
).18.
J. M.
Leclerq
, C.
Mijoule
, and P.
Yvan
, J. Chem. Phys.
64
, 1464
(1976
).19.
20.
C. E.
Dykstra
, R. R.
Lucchese
, and H. F.
Schaefer
III, J. Chem. Phys.
67
, 2422
(1977
).21.
L.
Serrano-Andres
, M.
Merchan
, I.
Nebot-Gill
, R.
Lindh
, and B. O.
Roos
, J. Chem. Phys.
98
, 3151
(1993
).22.
L.
Serrano-Andres
, B. O.
Ross
, and M.
Merchan
, Theor. Chim. Acta
87
, 387
(1994
).23.
K.
Nakayama
, H.
Nakano
, and K.
Hirao
, Int. J. Quantum Chem.
66
, 157
(1998
).24.
P. G.
Szalay
, A.
Karpfen
, and H.
Lischka
, Chem. Phys.
130
, 219
(1989
).25.
26.
C. E.
Dykstra
and H. F.
Schaefer
III, J. Am. Chem. Soc.
97
, 7210
(1975
).27.
F.
Aquilante
, V.
Barone
, and B. O.
Roos
, J. Chem. Phys.
119
, 12323
(2003
).28.
H. A.
Witek
, H.
Nakano
, and K.
Hirao
, J. Comput. Chem.
24
, 1390
(2003
).29.
M.
Boggio-Pasqua
, M. J.
Bearpark
, M.
Klene
, and M. A.
Robb
, J. Chem. Phys.
120
, 7849
(2004
).30.
31.
J.
Lappe
and R. J.
Cave
, J. Phys. Chem. A
104
, 2294
(2000
).32.
T.
Nakajima
and H.
Nakatsuji
, Chem. Phys. Lett.
280
, 79
(1997
);T.
Nakajima
and H.
Nakatsuji
,Chem. Phys.
242
, 177
(1999
).33.
M.
Ishida
, K.
Toyota
, M.
Ehara
, and H.
Nakatsuji
, Chem. Phys. Lett.
347
, 493
(2001
).34.
R.
Shepard
, H.
Lischka
, P. G.
Szalay
, T.
Kovar
, and M.
Ernzerhof
, J. Chem. Phys.
96
, 2085
(1992
);H.
Lischka
, M.
Dallos
, and R.
Shepard
, Mol. Phys.
100
, 1647
(2002
).35.
Y.
Luo
, H.
Ågren
, and S.
Stafström
, J. Chem. Phys.
98
, 7782
(1994
).36.
E.
Hollauer
and M. A. C.
Nascimento
, Chem. Phys. Lett.
181
, 463
(1991
).37.
D. W.
Turner
, Molecular Photoelectron Spectroscopy
(Wiley-Interscience
, New York, NY
, 1970
).38.
39.
H.
Nakatsuji
, Chem. Phys. Lett.
59
, 362
(1978
).40.
H.
Nakatsuji
, Chem. Phys. Lett.
67
, 329
(1979
).41.
H.
Nakatsuji
, Acta Chim. Hung.
129
, 719
(1992
);Computational Chemistry—Review of Current Trends
(World Scientific
, Singapore
, 1997
);M.
Ehara
, J.
Hasegawa
, and H.
Nakatsuji
, Theory and Applications of Computational Chemistry: The First 40 Years
, edited by C. E.
Dykstra
, G.
Fenking
, K. S.
Kim
, and G. E.
Scuseria
(Elsevier
, Holland
, 2005
).42.
M.
Ehara
, M.
Ishida
, K.
Toyota
, and H.
Nakatsuji
, Reviews in Modern Quantum Chemistry
, edited By K. D.
Sen
(World Scientific
, Singapore
, 2002
);M.
Ishida
, K.
Toyota
, M.
Ehara
, M. J.
Frisch
, and H.
Nakatsuji
, J. Chem. Phys.
120
, 2593
(2004
).
[PubMed]
43.
H.
Nakatsuji
, J. Am. Chem. Soc.
95
, 345
(1973
);H.
Nakatsuji
and T.
Koga
, The Force Concept in Chemistry
, edited by B. M.
Deb
(Van Nostrand Reinhold
, New York
, 1981
).44.
45.
T. H.
Dunning
and P. J.
Hay
, Methods of Electronic Structure Theory
(Plenum
, New York
, 1977
).46.
H.
Nakatsuji
, Chem. Phys.
75
, 425
(1983
).47.
Structure Data of Free Polyatomic Molecules
, Landolt-Bornstein, New Series, Group II
, Vol. 7
(Springer
, Berlin
, 1976
).48.
H.
Nakatsuji
, Chem. Phys. Lett.
177
, 331
(1991
).49.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
et al, GAUSSIAN 03, Gaussian, Inc.
, Pittsburgh, PA, 2003
.50.
K.
Kimura
, S.
Katsumata
, Y.
Achiba
, and S.
Iwata
, Handbook of Helium(He I) Photoelectron Spectra of Fundamental Organic Molecules. Ionization Energies, ab initio Assignments, and Valence Electronic Structure for 200 Molecules
(Japan Scientific Societies
, Tokyo, Japan
, 1981
).51.
B.
Ostojic
and W.
Domcke
, Chem. Phys.
269
, 1
(2001
).52.
C.-P.
Hsu
, S.
Hirata
, and M.
Head-Gordon
, J. Phys. Chem. A
105
, 451
(2001
).53.
J. P.
Doering
and R.
McDiarmid
, J. Chem. Phys.
75
, 2477
(1981
).54.
R. R.
Chadwick
, D. P.
Gerrity
, and B. S.
Hudson
, J. Chem. Phys.
95
, 7204
(1991
).55.
L.
Serrano-Andres
, J.
Sanchez-Mann
, and I.
Nebot-Gil
, J. Chem. Phys.
97
, 7499
(1992
).56.
C. R.
Brundle
and M. B.
Robin
, J. Am. Chem. Soc.
92
, 5550
(1970
).57.
R. J.
Buenker
, S.
Shih
, and S. D.
Peyerimhoff
, Chem. Phys. Lett.
44
, 385
(1976
).58.
A. G.
Robinson
, P. R.
Winter
, and T. S.
Zwier
, J. Chem. Phys.
116
, 7918
(2002
).59.
C. S.
Page
and M.
Olivucci
, J. Comput. Chem.
24
, 298
(2003
).60.
B. S.
Hudson
, B. E.
Kohler
, and K.
Schulten
, In Excited States
(Academic
, New York
, 1982
).61.
C. E.
Dykstra
and H. F.
Schaefer
III, J. Am. Chem. Soc.
98
, 401
(1976
).62.
C. E.
Bolm
and A.
Bauder
, Chem. Phys. Lett.
88
, 55
(1982
).63.
O.
Kitao
and H.
Nakatsuji
, J. Chem. Phys.
87
, 1169
(1987
);J.
Wan
, J.
Meller
, M.
Hada
, M.
Ehara
, and H.
Nakatsuji
, J. Chem. Phys.
113
, 7853
(2000
);J.
Wan
, M.
Hada
, M.
Ehara
, and H.
Nakatsuji
, J. Chem. Phys.
114
, 842
(2001
).64.
J. M.
Hollas
, Spectrochim. Acta
19
, 1425
(1963
).65.
M.
Ehara
, M.
Nakata
, and H.
Nakatsuji
, Mol. Phys.
104
, 971
(2006
).66.
67.
G.
Mackinney
and O.
Temmer
, J. Am. Chem. Soc.
70
, 3586
(1948
).68.
W.
Hug
, J.
Kuhn
, K. J.
Seibold
, H.
Labhart
, and G.
Wag-niere
, Helv. Chim. Acta
54
, 1451
(1971
).69.
M. B.
Robin
, Higher Excited States of Polyatomic Molecules
(Academic
, New York
, 1975
).70.
71.
H.
Kato
, H.
Konishi
, H.
Yamabe
, and T.
Yonezawa
, Bull. Chem. Soc. Jpn.
40
, 2761
(1967
).72.
G.
Herzberg
, Molecular Spectra and Structure III. Electronic Spectra and Electronic Structure of Polyatomic Molecules
(Van Nostrand
, New York
, 1966
).73.
J. C. D.
Brand
, Trans. Faraday Soc.
50
, 431
(1954
).74.
75.
F. W.
Briss
, B. D.
Braund
, A. R. H.
Cole
, R.
Engleman
, A. A.
Green
, S. M.
Jarpar
, R.
Nanes
, B. J.
Orr
, D. A.
Ramsay
, and J.
Szyszka
, Can. J. Phys.
55
, 390
(1977
).76.
77.
B. F.
Minaev
, D.
Jonsson
, and H. Å. P.
Norman
, Chem. Phys.
194
, 19
(1995
).78.
© 2006 American Institute of Physics.
2006
American Institute of Physics
You do not currently have access to this content.