Nonadiabatic first-principles molecular dynamics simulations have been performed of the photoexcited Watson-Crick guanine-cytosine (GC) DNA base pair in the gas phase and in aqueous solution. An excited state coupled proton-electron transfer (CPET) from G to C along the central hydrogen bond is observed upon excitation of the state initially localized on G. In the resulting charge transfer state a conical intersection between the excited state and the ground state is easily accessible. Therefore radiationless decay is fast, of the order of , followed by a rapid CPET back reaction retrieving the initial Watson-Crick structure. A detailed analysis of the mechanism of nonradiative decay suggests a biexponential behavior in which out-of-plane motion plays a special role for the longer decay component.
REFERENCES
1.
C. E.
Crespo-Hernández
, B.
Cohen
, P. M.
Hare
, and B.
Kohler
, Chem. Rev. (Washington, D.C.)
104
, 1977
(2004
).2.
T.
Gustavsson
, A.
Bányász
, E.
Lazzarotto
, D.
Markovitsi
, G.
Scalmani
, M. J.
Frisch
, V.
Barone
, and R.
Improta
, J. Am. Chem. Soc.
128
, 607
(2006
).3.
H.
Langer
and N. L.
Doltsinis
, Phys. Chem. Chem. Phys.
5
, 4516
(2003
).4.
H.
Langer
and N. L.
Doltsinis
, Phys. Chem. Chem. Phys.
6
, 2742
(2004
).5.
C. M.
Marian
, J. Phys. Chem. A
111
, 1545
(2007
).6.
A. L.
Sobolewski
and W.
Domcke
, Phys. Chem. Chem. Phys.
6
, 2763
(2004
).7.
A. L.
Sobolewski
, W.
Domcke
, and C.
Hättig
, Proc. Natl. Acad. Sci. U.S.A.
102
, 17903
(2005
).8.
W.
Domcke
, D. R.
Yarkony
, and H.
Köppel
, Conical Intersections: Electronic Structure, Dynamics and Spectroscopy
(World Scientific
, Singapore
, 2004
).9.
N.
Ismail
, L.
Blancafort
, M.
Olivucci
, B.
Kohler
, and M. A.
Robb
, J. Am. Chem. Soc.
124
, 6818
(2002
).10.
M.
Merchán
and L.
Serrano-Andrés
, J. Am. Chem. Soc.
125
, 8108
(2003
).11.
S.
Matsika
, J. Phys. Chem. A
108
, 7584
(2004
).12.
S.
Perun
, A. L.
Sobolewski
, and W.
Domcke
, J. Phys. Chem. A
110
, 13238
(2006
).13.
M. Z.
Zgierski
, S.
Patchkovskii
, T.
Fujiwara
, and E. C.
Lim
, J. Phys. Chem. A
109
, 9384
(2005
).14.
H.
Chen
and S.
Li
, J. Phys. Chem. A
110
, 12360
(2006
).15.
S.
Perun
, A. L.
Sobolewski
, and W.
Domcke
, Chem. Phys.
313
, 107
(2005
).16.
T.
Schultz
, E.
Samoylova
, W.
Radloff
, I. A.
Hertel
, A. L.
Sobolewski
, and W.
Domcke
, Science
306
, 1765
(2004
).17.
A.
Abo-Rizio
, L.
Grace
, E.
Nir
, M.
Kabelac
, P.
Hobza
, and M. S.
de Vries
, Proc. Natl. Acad. Sci. U.S.A.
102
, 20
(2005
).18.
S.
Perun
, A. L.
Sobolewski
, and W.
Domcke
, J. Phys. Chem. A
110
, 9031
(2006
).19.
P.
Markwick
, N. L.
Doltsinis
, and J.
Schlitter
, J. Chem. Phys.
126
, 045104
(2007
).20.
N. L.
Doltsinis
and D.
Marx
, Phys. Rev. Lett.
88
, 166402
(2002
).21.
N. L.
Doltsinis
and D.
Marx
, J. Theor. Comput. Chem.
1
, 319
(2002
).22.
J. C.
Tully
, J. Chem. Phys.
93
, 1061
(1990
).23.
I.
Frank
, J.
Hutter
, D.
Marx
, and M.
Parrinello
, J. Chem. Phys.
108
, 4060
(1998
).24.
S.
Grimm
, C.
Nonnenberg
, and I.
Frank
, J. Chem. Phys.
119
, 11574
(2003
).25.
S.
Grimm
, C.
Nonnenberg
, and I.
Frank
, J. Chem. Phys.
119
, 11585
(2003
).26.
N. L.
Doltsinis
, Mol. Phys.
102
, 499
(2004
).27.
H.
Langer
, N. L.
Doltsinis
, and D.
Marx
, ChemPhysChem
6
, 1734
(2005
).28.
H.
Langer
and N. L.
Doltsinis
, J. Chem. Phys.
118
, 5400
(2003
).29.
J.
Hutter
, P.
Ballone
, M.
Bernasconi
, P.
Focher
, E.
Fois
, S.
Goedecker
, D.
Marx
, M.
Parrinello
, and M.
Tuckerman
, CPMD 3.4 (MPI für Festkörperforschung
, Stuttgart and IBM Zurich Research Laboratory).30.
D.
Marx
and J.
Hutter
, in Modern Methods and Algorithms of Quantum Chemistry
, edited by J.
Grotendorst
(NIC
, Jülich
, 2000
);31.
S.
Nosé
, J. Chem. Phys.
81
, 511
(1984
).32.
W. G.
Hoover
, Phys. Rev. A
31
, 1695
(1985
).33.
A. D.
Becke
, Phys. Rev. A
38
, 3098
(1988
).34.
C.
Lee
, W.
Yang
, and R. C.
Parr
, Phys. Rev. B
37
, 785
(1988
).35.
N.
Troullier
and J. L.
Martins
, Phys. Rev. B
43
, 1993
(1991
).36.
N. L.
Doltsinis
, in Computational Nanoscience: Do it Yourself!
, edited by J.
Grotendorst
, S.
Blügel
, and D.
Marx
(NIC
, FZ Jülich
, 2006
); www.fz-juelich.de/nic-series/volume31/doltsinis1.pdf37.
G.
Groenhof
, L. V.
Schäfer
, H.
Grubmüller
, M.
Boggio-Pasqua
, and M. A.
Robb
, J. Am. Chem. Soc.
(to be published).© 2007 American Institute of Physics.
2007
American Institute of Physics
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