Molecular dynamics simulations of the rhodopsin photoreaction reveal coherent low frequency oscillations in the primary photoproduct (photorhodopsin), with frequencies slightly higher than observed in the experiment. The coherent molecular motions in the batho-precursor can be attributed to the activation of ground state vibrational modes in the hot photo-product, involving out-of-plane deformations of the carbon skeleton. Results are discussed and compared with respect to spectroscopic data and suggested reaction mechanisms.
REFERENCES
1.
J.
Bockaert
, G.
Roussignol
, C.
Bécamel
, S.
Gavarini
, L.
Joubert
, A.
Dumuis
, L.
Fagni
et al., Biochem. Soc. Trans.
32
, 851
(2004
).2.
W. J.
DeGrip
and K. J.
Rothschild
, Molecular Mechanisms of Visual Transduction
(Elsevier
, Amsterdam, The Netherlands
, 2000
).3.
H.
Kandori
, Y.
Shichida
, and T.
Yoshizawa
, Biochem.
66
, 1197
(2001
).4.
O.
Weingart
, J. Am. Chem. Soc.
129
, 10618
(2007
).5.
O.
Weingart
, Chem. Phys.
349
, 348
(2008
).6.
O.
Weingart
, P.
Altoè
, M.
Stenta
, A.
Bottoni
, G.
Orlandi
, and M.
Garavelli
, Phys. Chem. Chem. Phys.
13
, 3645
(2011
).7.
J.
Fan
, B.
Rohrer
, G.
Moiseyev
, J.-X.
Ma
, and R. K.
Crouch
, Proc. Natl. Acad. Sci. U.S.A.
, 100
, 13662
(2003
).8.
R. R.
Birge
, C. M.
Einterz
, H. M.
Knapp
, and L. P.
Murray
, Biophys. J.
53
, 367
(1988
).9.
S.
Hahn
and G.
Stock
, J. Phys. Chem. B
104
, 1146
(2000
).10.
A.
Bifone
, H. J. M.
de Groot
, and F.
Buda
, Chem. Phys. Lett.
248
, 165
(1996
).11.
S.
Sekharan
, O.
Weingart
, and V.
Buss
, Biophys. J.
91
, L7
(2006
).12.
A.
Cembran
, F.
Bernardi
, M.
Olivucci
, and M.
Garavelli
, Proc. Natl. Acad. Sci. U.S.A.
102
, 6255
–60
(2005
).13.
R.
González-Luque
, M.
Garavelli
, F.
Bernardi
, M.
Merchan
, M. A.
Robb
, and M.
Olivucci
, Proc. Natl. Acad. Sci. U.S.A.
97
, 9379
(2000
).14.
S.
Fantacci
, A.
Migani
, and M.
Olivucci
, J. Phys. Chem. A
108
, 1208
(2003
).15.
S.
Hayashi
, E.
Tajkhorshid
, and K.
Schulten
, Biophys. J.
96
, 403
(2009
).16.
A.
Strambi
, P. B.
Coto
, L. M.
Frutos
, N.
Ferré
, and M.
Olivucci
, J. Am. Chem. Soc.
130
, 3382
(2008
).17.
L. M.
Frutos
, T.
Andruniów
, F.
Santoro
, N.
Ferré
, and M.
Olivucci
, Proc. Natl. Acad. Sci. U.S.A.
104
, 7764
(2007
).18.
D.
Polli
, P.
Altoè
, O.
Weingart
, K. M.
Spillane
, C.
Manzoni
, D.
Brida
, G.
Tomasello
et al., Nature (London)
467
, 440
(2010
).19.
C.
Punwong
, Ph.D. dissertation (University of Illinois at Urbana-Champaign
, 2009
).20.
A.
Virshup
, C.
Punwong
, T.
Pogorelov
, B. A.
Lindquist
, C.
Ko
, and T. J.
Martinez
, J. Phys. Chem. B
113
, 3280
(2009
).21.
Q.
Wang
, R. W.
Schoenlein
, L. A.
Peteanu
, R. A.
Mathies
, and C. V.
Shank
, Science
266
, 422
(1994
).22.
Recently, a low frequency oscillation was reported in a single long running trajectory of a retinal chromophore mimic started at 0 K. The origin of this oscillation, which was associated to a vibrational coherence experimentally recorded in the photoproduct signal, was attributed to a vibration modulating the orientation of the two chromophore halves, see
M.
Olivucci
, “New QM/MM opportunities for in silico macromolecular photochemistry
,” Invited Talk at the CECAM Workshop
, Lyon, France
, 28 February–2 March 2012
and Ref. 33.23.
P.
Altoè
, M.
Stenta
, A.
Bottoni
, and M.
Garavelli
, Theor. Chem. Acc.
118
, 219
(2007
).24.
T.
Okada
, M.
Sugihara
, A.-N.
Bondar
, M.
Elstner
, P.
Entel
, and V.
Buss
, J. Mol. Biol.
342
, 571
(2004
).25.
D. A.
Case
, T. A.
Darden
, I.
Cheatham
, C. L.
Simmerling
, J.
Wang
, R. E.
Duke
, R.
Luo
et al., AMBER 9
(University of California
, San Francisco
, 2006
).26.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
et al., GAUSSIAN 03, Revision C.02, Gaussian, Inc., Wallingford, CT, 2004
.27.
H.-J.
Werner
, P. J.
Knowles
, R.
Lindh
, F. R.
Manby
, M.
Schütz
et al., MOLPRO, version 2008.1, a package of ab initio programs, 2008
, see http://www.molpro.net.28.
J. C.
Tully
, Int. J. Quant. Chem.
40
, 299
(1991
).29.
G.
Granucci
and M.
Persico
, J. Chem. Phys.
126
, 134114
(2007
).30.
F. L.
Gervasio
, G.
Cardini
, P. R.
Salvi
, V.
Schettino
, S.
Molecolare
, D.
Chimica
, and V. G.
Capponi
, J. Phys. Chem. A
102
, 2131
(1998
).31.
J.
Briand
, O.
Bräm
, J.
, Réhault
, J.
Léonard
, A.
Cannizzo
, M.
Chergui
, V.
Zanirato
, M.
Olivucci
, J.
Helbing
, and S.
Haacke
, Phys. Chem. Chem. Phys.
12
, 3178
(2010
).32.
A. D.
Dunkelberger
, R. D.
Kieda
, J. Y.
Shin
, R. R.
Paccani
, S.
Fusi
, M.
Olivucci
, and F. F.
Crim
, J. Phys. Chem. A
116
, 3527
(2012
).33.
J.
Léonard
, I.
Schapiro
, J.
Briand
, S.
Fusi
, R.
Rossi Paccani
, M.
Olivucci
, and S.
Haacke
, “Mechanistic origin of the vibrational coherence accompanying the photoreaction of biomimetic molecular switches
,” Chem. Europ. J.
(in press).© 2012 American Institute of Physics.
2012
American Institute of Physics
You do not currently have access to this content.