The effect of electronic-nuclear coupling on electronic transport through a complex molecular network is studied. Electronic tunneling dynamics in a network of N donor/acceptor sites, connected by molecular bridges, is shown to be controlled by electronic-nuclear coupling at the bridges. Particularly, electronic coupling to an accepting nuclear mode at the contact site between the donor and the rest of the network is shown to affect the tunneling path selection to specific acceptors. In the “deep” tunneling regime, the network is mapped onto an N-level system using a recursive perturbation expansion, enabling analytical treatment of the electronic dynamics. The analytic formulation is applied for two model systems, demonstrating site-directed tunneling by electronic-nuclear coupling. Numerical simulations suggest that this phenomenon is not limited to the deep tunneling regime.

1.
V.
May
and
O.
Kühn
,
Charge and Energy Transfer Dynamics in Molecular Systems: A Theoretical Introduction
(
Wiley-VCH
,
Berlin
,
2000
).
2.
D. N.
Beratan
,
J. N.
Onuchic
,
J. N.
Betts
,
B. E.
Bowler
, and
H. B.
Gray
,
J. Am. Chem. Soc.
112
,
7915
(
1990
).
3.
D. N.
Beratan
,
J. N.
Onuchic
,
J. R.
Winkler
, and
H. B.
Gray
,
Science
258
,
1740
(
1992
).
4.
K. D.
Jordan
and
M. N.
Paddon-Row
,
Chem. Rev. (Washington, D.C.)
92
,
395
(
1992
).
5.
C.
Liang
and
M. D.
Newton
,
J. Phys. Chem.
96
,
2855
(
1992
).
6.
O. G.
Poluektov
,
S. V.
Paschenko
,
L. M.
Utschig
,
K. V.
Lakshmi
, and
M. C.
Thurnauer
,
J. Am. Chem. Soc.
127
,
11910
(
2005
).
7.
C.
Kirmaier
,
J. A.
Bautista
,
P. D.
Laible
,
D. K.
Hanson
, and
D.
Holten
,
J. Phys. Chem. B
109
,
24160
(
2005
).
8.
M. R.
Gunner
,
A.
Nicholls
, and
B.
Honig
,
J. Phys. Chem.
100
,
4277
(
1996
).
9.
S. L.
Gould
,
G.
Kodis
,
R. E.
Palacios
,
L.
de la Garza
,
A.
Elrune
,
D.
Gust
,
T. A.
Moore
, and
A. L.
Moore
,
J. Phys. Chem. B
108
,
10566
(
2004
).
10.
A.
Sautter
,
B. K.
Kaletas
,
D. G.
Schmid
,
R.
Dobrawa
,
M.
Zimine
,
G.
Jung
,
I. H. M.
van Stokkum
,
L.
De Cola
,
R. M.
Williams
, and
F.
Würthner
,
J. Am. Chem. Soc.
127
,
6719
(
2005
).
11.
K. R. J.
Thomas
,
A. L.
Thompson
,
A. V.
Sivakumar
,
C. J.
Bardeen
, and
S.
Thayumanavan
,
J. Am. Chem. Soc.
127
,
373
(
2005
).
12.
O. S.
Wenger
,
B. S.
Leigh
,
R. M.
Villahermosa
,
H. B.
Gray
, and
J. R.
Winkler
,
Science
307
,
99
(
2005
).
13.
S. D.
Wettig
,
G. A.
Bare
,
R. J. S.
Skinner
, and
J. S.
Lee
,
Nano Lett.
3
,
617
(
2003
).
14.
S. D.
Straight
,
J.
Andreasson
,
G.
Kodis
,
A. L.
Moore
,
T. A.
Moore
, and
D.
Gust
,
J. Am. Chem. Soc.
127
,
2717
(
2005
).
15.
S.
Lukas
,
S. E.
Miller
, and
M. R.
Wasielewski
,
J. Phys. Chem. B
104
,
931
(
2000
).
16.
S.
Lukas
,
P. J.
Bushard
, and
M. R.
Wasielewski
,
J. Phys. Chem. A
106
,
2074
(
2002
).
17.
Y. Q.
Gao
and
R. A.
Marcus
,
J. Phys. Chem. A
106
,
1956
(
2002
).
18.
M.
Caspary
and
U.
Peskin
,
J. Chem. Phys.
123
,
151101
(
2005
).
19.
E. S.
Madvedev
and
A. A.
Stuchebrukhov
,
J. Chem. Phys.
107
,
3821
(
1997
).
20.
A. K.
Felts
,
W. T.
Pollard
, and
R. A.
Friesner
,
J. Chem. Phys.
99
,
2929
(
1995
).
21.
S. S.
Skourtis
and
S.
Mukamel
,
Chem. Phys.
197
,
367
(
1995
).
22.
O.
Kuehn
,
V.
Rupasov
, and
S.
Mukamel
,
J. Chem. Phys.
104
,
5821
(
1996
).
23.
W. B.
Davis
,
M. R.
Wasielewski
,
M. A.
Ratner
,
V.
Mujica
, and
A.
Nitzan
,
J. Phys. Chem. A
101
,
6158
(
1997
).
24.
D.
Segal
,
A.
Nitzan
,
W. B.
Davis
,
M. R.
Wasielewski
, and
M. A.
Ratner
,
J. Phys. Chem. B
104
,
3817
(
2000
).
25.
M.
Bixon
and
J.
Jortner
,
J. Chem. Phys.
107
,
5154
(
1997
).
26.
Q.
Xie
,
G.
Archontis
, and
S. S.
Skourtis
,
Chem. Phys. Lett.
312
,
237
(
1999
).
27.
S. S.
Skourtis
,
G.
Archontis
, and
Q.
Xie
,
J. Chem. Phys.
115
,
9444
(
2001
).
28.
E. G.
Petrov
,
Y. R.
Zelinskyy
, and
V.
May
,
J. Phys. Chem. B
106
,
3092
(
2002
).
29.
H.
Ness
and
A. J.
Fisher
,
Phys. Rev. Lett.
83
,
452
(
1999
).
30.
H.
Ness
,
S. A.
Shevlin
, and
A. J.
Fisher
,
Phys. Rev. B
63
,
125422
(
2001
).
31.
A.
Troisi
,
A.
Nitzan
, and
M. A.
Ratner
,
J. Chem. Phys.
119
,
5782
(
2003
).
32.
S. S.
Skourtis
,
D. H.
Waldeck
, and
D. N.
Beratan
,
J. Phys. Chem. B
108
,
15511
(
2004
).
33.
M.
A-Hilu
and
U.
Peskin
,
Chem. Phys.
296
,
231
(
2004
).
34.
M.
A-Hilu
and
U.
Peskin
,
J. Chem. Phys.
122
,
021103
(
2005
).
35.
A.
Malka
and
U.
Peskin
,
Isr. J. Chem.
45
,
217
(
2005
).
36.
D.
Brisker
and
U.
Peskin
,
J. Chem. Phys.
125
,
111103
(
2006
).
You do not currently have access to this content.