Vertical and adiabatic excitation energies of the lowest excited state in the water-hydroxyl complex have been determined using coupled cluster, multireference configuration interaction, multireference perturbation theory, and density-functional methods. A significant redshift of about in the vertical excitation energy of the complex compared to that of the hydroxyl radical monomer is found with the coupled cluster calculations validating previous results. Electronic excitation leads to a structure with near-equal sharing of the hydroxyl hydrogen by both oxygen atoms and a concomitantly large redshift of the adiabatic excitation energy of approximately relative to the vertical excitation energy. The combination of redshifts ensures that the electronic transition in the complex lies well outside the equivalent excitation in the hydroxyl radical monomer. The complex is approximately five times more strongly bound in the excited state than in the ground state.
REFERENCES
1.
S.
Aloisio
and J. S.
Francisco
, Acc. Chem. Res.
33
, 825
(2000
).2.
V.
Vaida
, H. G.
Kjaergaard
, and K. J.
Feierabend
, Int. Rev. Phys. Chem.
22
, 203
(2003
).3.
D. P.
Schofield
and H. G.
Kjaergaard
, J. Chem. Phys.
120
, 6930
(2004
).4.
5.
A.
Engdahl
, G.
Karlström
, and B.
Nelander
, J. Chem. Phys.
118
, 7797
(2003
).6.
V. S.
Langford
, A. J.
McKinley
, and T. I.
Quickenden
, J. Am. Chem. Soc.
122
, 12859
(2000
).7.
P. D.
Cooper
, H. G.
Kjaergaard
, V. S.
Langford
, A. J.
McKinley
, T. I.
Quickenden
, and D. P.
Schofield
, J. Am. Chem. Soc.
125
, 6048
(2003
).8.
K. S.
Kim
, H. S.
Kim
, J. H.
Jang
, H. S.
Kim
, B.-J.
Mhin
, Y.
Xie
, and H. F.
Schaefer
, J. Chem. Phys.
94
, 2057
(1991
).9.
Y.
Xie
and H. F.
Schaefer
, J. Chem. Phys.
98
, 8829
(1993
).10.
Y.
Ohshima
, K.
Sato
, Y.
Sumiyoshi
, and Y.
Endo
, J. Am. Chem. Soc.
127
, 1108
(2005
).11.
C. S.
Brauer
, G.
Sedo
, E. M.
Grumstrup
, K. R.
Leopold
, M. D.
Marshall
, and H. O.
Leung
, Chem. Phys. Lett.
401
, 420
(2005
).12.
M. D.
Marshall
and M. I.
Lester
, J. Phys. Chem. B
109
, 8400
(2005
).13.
T.
Brauers
, M.
Hausmann
, A.
Bister
, A.
Kraus
, and H.-P.
Dorn
, J. Geophys. Res.
106
, 7399
(2001
).14.
J. F.
Stanton
and R. J.
Bartlett
, J. Chem. Phys.
98
, 7029
(1993
).15.
C. E.
Smith
, R. A.
King
, and T. D.
Crawford
, J. Chem. Phys.
122
, 054110
(2005
).16.
K.
Andersson
, P.-Å.
Malmqvist
, B. O.
Roos
, A. J.
Sadlej
, and K.
Wolinski
, J. Phys. Chem.
94
, 5483
(1990
).17.
K.
Andersson
, P.-Å.
Malmqvist
, and B. O.
Roos
, J. Chem. Phys.
96
, 1218
(1992
).18.
B.
Roos
, M.
Fülscher
, P.-Å.
Malmqvist
, M.
Merchán
, and L.
Serrano-Andrés
, in Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy
, edited by S.
Langhoff
(Kluwer Academic
, Dordrecht
, 1995
), pp. 357
–438
.19.
T. D.
Crawford
and H. F.
Schaefer
, in Reviews in Computational Chemistry
, edited by K. B.
Lipkowitz
and D. B.
Boyd
(VCH
, New York
, 2000
), Vol. 14
, Chap. 2, pp. 33
–136
.20.
C. D.
Sherrill
and H. F.
Schaefer
, Adv. Quantum Chem.
34
, 143
(1999
).21.
R. G.
Parr
and W.
Yang
, Density-Functional Theory of Atoms and Molecules
(Oxford University
, New York
, 1989
).22.
M. E.
Casida
, in Recent Advances in Density Functional Methods
, edited by D. P.
Chong
(World Scientific
, Singapore
, 1995
), Vol. 1
.23.
R.
Bauernschmitt
and R.
Ahlrichs
, Chem. Phys. Lett.
256
, 454
(1996
).24.
T. H.
Dunning
, J. Chem. Phys.
90
, 1007
(1989
).25.
R. A.
Kendall
, T. H.
Dunning
, and R. J.
Harrison
, J. Chem. Phys.
96
, 6796
(1992
).26.
T. W.
Robinson
, D. P.
Schofield
, and H. G.
Kjaergaard
, J. Chem. Phys.
118
, 7226
(2003
).27.
K.
Raghavachari
, G. W.
Trucks
, J. A.
Pople
, and M.
Head-Gordon
, Chem. Phys. Lett.
157
, 479
(1989
).28.
R. J.
Bartlett
, J. D.
Watts
, S. A.
Kucharski
, and J.
Noga
, Chem. Phys. Lett.
165
, 513
(1990
);R. J.
Bartlett
, J. D.
Watts
, S. A.
Kucharski
, and J.
Noga
, Chem. Phys. Lett.
167
, 609
(1990
).29.
A. D.
Becke
, J. Chem. Phys.
98
, 5648
(1993
).30.
C.
Lee
, W.
Yang
, and R. G.
Parr
, Phys. Rev. B
37
, 785
(1988
).31.
J.
Gauss
, W. J.
Lauderdale
, J. F.
Stanton
, J. D.
Watts
, and R. J.
Bartlett
, Chem. Phys. Lett.
182
, 207
(1991
).32.
J.
Gauss
, J. F.
Stanton
, and R. J.
Bartlett
, J. Chem. Phys.
95
, 2623
(1991
).33.
J. F.
Stanton
and J.
Gauss
, J. Chem. Phys.
99
, 8840
(1993
).34.
T. D.
Crawford
, C. D.
Sherrill
, E. F.
Valeev
et al., PSI 3.2, 2003
.35.
J. F.
Stanton
, J.
Gauss
, J. D.
Watts
, W. J.
Lauderdale
, and R. J.
Bartlett
, ACES II, 1993
. The package also contains modified versions of the MOLECULE Gaussian integral program of J. Almlöf and P. R. Taylor, the ABACUS integral derivative program written by T. U. Helgaker, H. J. Aa. Jensen, P. Jørgensen, and P. R. Taylor, and the PROPS property evaluation integral code of P. R. Taylor.36.
R. D.
Amos
, A.
Bernhardsson
et al., MOLPRO, a package of ab initio programs designed by H. J. Werner and P. J. Knowles, Version 2002.6, 2002
.37.
R.
Ahlrichs
, M.
Bärand
, H.-P.
Baron
et al., TURBOMOLE v5.6, 2002
.38.
S.
Du
, J. S.
Francisco
, G. K.
Schenter
, T. D.
Iordanov
, B. C.
Garrett
, M.
Dupuis
, and J.
Li
, J. Chem. Phys.
124
, 224318
(2006
).39.
H. G.
Kjaergaard
, J. Phys. Chem. A
106
, 2979
(2002
).40.
H. G.
Kjaergaard
, T. W.
Robinson
, D. L.
Howard
, J. S.
Daniel
, J. A.
Headrick
, and V.
Vaida
, J. Phys. Chem. A
107
, 10680
(2003
).41.
J. R.
Roscioli
, E. G.
Diken
, M. A.
Johnson
, S.
Horvath
, and A. B.
McCoy
, J. Phys. Chem. A
110
, 4943
(2006
).42.
T. J.
Lee
and P. R.
Taylor
, Int. J. Quantum Chem., Quantum Chem. Symp.
23
, 199
(1989
).43.
J.
Gillis
, A.
Goldman
, G.
Stark
, and C.
Rinsland
, J. Quant. Spectrosc. Radiat. Transf.
68
, 225
(2000
).© 2006 American Institute of Physics.
2006
American Institute of Physics
You do not currently have access to this content.
