Ultrafast pump–probe measurements on the electron donor–acceptor complex of tetracyanoethylene with hexamethylbenzene in polar and nonpolar solvents are reported. Ground state coherence in the complex stretching mode at 165 cm−1 excited by impulsive stimulated Raman scattering is observed as well as decay of the ground state bleaching signal due to return electron transfer to the ground state. The experimental electron‐transfer rates are compared with nonadiabatic and adiabatic electron‐transfer theories using a previously published analysis of all the vibrational modes active in the reaction. It is shown that a breakdown of the Born–Oppenheimer approximation can give rise to a coupling that leads to the observed electron‐transfer reaction. The non‐Born–Oppenheimer matrix element is estimated using information obtained from the absorption and Raman spectra. Using this coupling, good agreement is found between the experimentally observed and theoretically predicted rates. Caveats of the various theories, the reliability of the normal mode analysis, and aspects of electron transfer that theory should address are discussed.

1.
R. A.
Marcus
and
N.
Sutin
,
Biochim. Biophys. Acta
811
,
265
(
1986
).
2.
J.
Jortner
,
J. Chem. Phys.
64
,
4860
(
1976
).
3.
(a) G. Briegleb, Elektronen-Donator-Acceptor-Komplexe (Springer, Berlin, 1961);
(b) R. S. Mulliken and W. B. Person, Molecular Complexes (Wiley, New York, 1969);
(c) N. Mataga and T. Kubota, Molecular Interactions and Electronic Spectra (Dekker, New York, 1970).
4.
T.
Asahi
and
N.
Mataga
,
J. Phys. Chem.
95
,
1956
(
1991
).
5.
T.
Asahi
and
N.
Mataga
,
J. Phys. Chem.
93
,
6575
(
1989
).
6.
S.
Ojima
,
H.
Miyasaka
, and
N.
Mataga
,
J. Phys. Chem.
94
,
4147
(
1990
).
7.
S.
Ojima
,
H.
Miyasaka
, and
N.
Mataga
,
J. Phys. Chem.
94
,
7534
(
1990
).
8.
H.
Sumi
and
R. A.
Marcus
,
J. Chem. Phys.
84
,
4894
(
1986
).
9.
J.
Jortner
and
M.
Bixon
,
J. Chem. Phys.
88
,
167
(
1988
).
10.
T.
Kobayashi
,
Y.
Takagi
,
H.
Kandori
,
K.
Kemnitz
, and
K.
Yoshihara
,
Chem. Phys. Lett.
180
,
416
(
1991
).
11.
S. K.
Doorn
,
R. L.
Blackbourn
,
C. S.
Johnson
, and
J. T.
Hupp
,
Electrochim. Acta
36
,
1775
(
1991
).
12.
F.
Markel
,
N. S.
Ferris
,
I. R.
Gould
, and
A. B.
Myers
,
J. Am. Chem. Soc.
114
,
6208
(
1992
).
13.
K. H.
Michaelian
,
K. E.
Rieckhoff
, and
E. M.
Voigt
,
Chem. Phys. Lett.
23
,
5
(
1973
).
14.
K. H.
Michaelian
,
K. E.
Rieckhoff
, and
E. M.
Voigt
,
Chem. Phys. Lett.
39
,
521
(
1976
).
15.
M.
Tahara
,
S.
Matsuzaki
, and
S.
Maeda
,
Bull. Chem. Soc. Jpn.
51
,
2735
(
1978
).
16.
M. L.
Smith
and
J. L.
McHale
,
J. Phys. Chem.
89
,
4002
(
1985
).
17.
J. L.
McHale
and
M. J.
Merriam
,
J. Phys. Chem.
93
,
526
(
1989
).
18.
B. M.
Britt
,
H. B.
Lueck
, and
J. L.
McHale
,
Chem. Phys. Lett.
190
,
528
(
1992
).
19.
I. R.
Gould
,
D.
Noukakis
,
J. L.
Goodman
,
R. H.
Young
, and
S.
Farid
,
J. Am. Chem. Soc.
115
,
3830
(
1993
).
20.
I. R.
Gould
,
D.
Noukakis
,
L.
Gomez-Jahn
,
J. L.
Goodman
, and
S.
Farid
,
J. Am. Chem. Soc.
115
,
4405
(
1993
).
21.
I. R.
Gould
,
D.
Noukakis
,
L.
Gomez-Jahn
,
R. H.
Young
,
J. L.
Goodman
, and
S.
Farid
,
Chem. Phys.
176
,
439
(
1993
).
22.
D. L.
Jeanmaire
,
M. R.
Suchanski
, and
R. P.
van Duyne
,
J. Am. Chem. Soc.
97
,
1699
(
1975
).
23.
K.
Wynne
,
C.
Galli
, and
R. M.
Hochstrasser
,
Chem. Phys. Lett.
193
,
17
(
1992
).
24.
R. J.
Sension
,
A. Z.
Szarka
, and
R. M.
Hochstrasser
,
J. Chem. Phys.
97
,
5239
(
1992
).
25.
D.
Ben-Amotz
and
C. B.
Harris
,
J. Chem. Phys.
86
,
4856
(
1987
).
26.
G. C.
Walker
,
E.
Åkeson
,
A. E.
Johnson
,
N. E.
Levinger
, and
P. F.
Barbara
,
J. Phys. Chem.
96
,
3728
(
1992
).
27.
K.
Tominaga
,
D. A. V.
Kliner
,
A. E.
Johnson
,
N. E.
Levinger
, and
P. F.
Barbara
,
J. Chem. Phys.
98
,
1228
(
1993
).
28.
P. F.
Barbara
and
W.
Jarzeba
,
Adv. Photochem.
15
,
1
(
1990
).
29.
N. S.
Hush
,
Electrochim. Acta
13
,
1005
(
1968
).
30.
J. R.
Piatt
,
J. Chem. Phys.
17
,
484
(
1949
).
31.
W.
Moffitt
,
J. Chem. Phys.
22
,
320
(
1954
).
32.
M.
Rossi
,
U.
Buser
, and
E.
Haselbach
,
Helv. Chim. Acta
59
,
1039
(
1976
).
33.
J.
Cioslowski
,
Tetrahedron
42
,
735
(
1986
).
34.
M.
Saheki
,
H.
Yamada
,
H.
Yoshioka
, and
K.
Nakatsu
,
Acta Cryst. B
32
,
662
(
1976
).
35.
(a)
M.
Saheki
,
H.
Yamada
,
H.
Yoshioka
, and
K.
Nakatsu
,
Acta Cryst. B
32
,
662
(
1976
);
(b)
E.
Maverick
,
K. N.
Trueblood
, and
D. A.
Bekoe
,
Acta Cryst. B
34
,
2777
(
1978
).
36.
W.
Liptay
,
T.
Rehm
,
D.
Wehning
,
L.
Schanne
,
W.
Baumann
, and
W.
Lang
,
Z. Naturforsch. Teil A
37
,
1427
(
1982
).
37.
C. W.
Jurgensen
,
M. J.
Peanasky
, and
H. G.
Drickamer
,
J. Chem. Phys.
83
,
6108
(
1985
).
38.
G.
van der Zwan
and
J. T.
Hynes
,
J. Phys. Chem.
89
,
4181
(
1985
).
39.
L. C.
Emery
and
W. D.
Edwards
,
Int. J. Quantum Chem., Quantum Chem. Symp.
25
,
347
(
1991
).
40.
M.
Rossi
and
E.
Haselbach
,
Helvetica Chimica Acta
62
,
140
(
1979
).
41.
A. G.
Redfield
,
Adv. Mag. Res.
1
,
1
(
1965
).
42.
J.
Jortner
,
S. A.
Rice
, and
R. M.
Hochstrasser
,
Adv. Photochem.
7
,
149
(
1969
).
43.
C. C.
Moser
,
J. M.
Keske
,
K.
Warncke
,
R. S.
Farid
, and
P. L.
Dutton
,
Nature (London)
355
,
796
(
1992
).
44.
S.
Efrima
and
M.
Bixon
,
J. Chem. Phys.
64
,
3639
(
1976
).
45.
S.
Efrima
and
M.
Bixon
,
Chem. Phys.
13
,
447
(
1976
).
46.
Y. J.
Yan
and
S.
Mukamel
,
J. Chem. Phys.
85
,
5908
(
1986
).
47.
A. B. Myers and R. A. Mathies, Biological Applications of Raman Spectroscopy, edited by T. G. Spiro (Wiley, New York, 1987).
48.
L. D.
Zusman
,
Chem. Phys.
49
,
295
(
1980
).
49.
T.
Fonseca
,
J. Chem. Phys.
91
,
2869
(
1989
).
50.
M.
Sparpaglione
and
S.
Mukamel
,
J. Chem. Phys.
88
,
3263
(
1988
).
51.
J.
Tang
and
J. R.
Norris
,
Chem. Phys.
175
,
337
(
1993
).
52.
A. I.
Burshtein
,
P. A.
Frantsuzov
, and
A. A.
Zharikov
,
J. Chem. Phys.
96
,
4261
(
1992
).
53.
M.
Bixon
and
J.
Jortner
,
Chem. Phys.
176
,
467
(
1993
).
54.
P. F.
Barbara
,
G. C.
Walker
, and
T. P.
Smith
,
Science
256
,
975
(
1992
).
55.
E.
Åkeson
,
G. C.
Walker
, and
P. F.
Barbara
,
J. Chem. Phys.
95
,
4188
(
1991
).
56.
K. F. Freed, in Radiationless Processes in Molecules and Condensed Phases, edited by F. K. Fong (Springer, Berlin, 1976).
57.
K. V.
Reddy
,
D. F.
Heller
, and
M. J.
Berry
,
J. Chem. Phys.
76
,
2814
(
1982
).
58.
J. W.
Perry
and
A. H.
Zewail
,
J. Phys. Chem.
85
,
933
(
1981
).
59.
E. L.
Sibert
III
,
W. P.
Reichardt
, and
J. T.
Hynes
,
J. Chem. Phys.
81
,
1115
(
1984
).
60.
R.
Kubo
,
J. Phys. Soc. Jpn.
17
,
1100
(
1962
).
61.
Y. J.
Yan
and
S.
Mukamel
,
Phys. Rev. A
41
,
6485
(
1990
).
62.
Y. J.
Yan
and
S.
Mukamel
,
J. Chem. Phys.
89
,
5160
(
1988
).
63.
S.
Chandrasekhar
,
Rev. Mod. Phys.
15
,
1
(
1943
).
64.
N.
Agmon
and
J. J.
Hopfield
,
J. Chem. Phys.
78
,
6947
(
1983
).
65.
B.
Bagchi
and
G. R.
Fleming
,
J. Phys. Chem.
94
,
9
(
1990
).
66.
B. R.
Henry
and
W. R. A.
Greenlay
,
J. Chem. Phys.
72
,
5516
(
1980
).
67.
M. J.
Weaver
and
G. E.
McManis
,
Acc. Chem. Res.
23
,
294
(
1990
).
68.
M.
Maroncelli
,
J. Chem. Phys.
94
,
2084
(
1991
).
69.
E. A.
Carter
and
J. T.
Hynes
,
J. Chem. Phys.
94
,
5961
(
1991
).
70.
S. J.
Rosenthal
,
X.
Xie
,
M.
Du
, and
G. R.
Fleming
,
J. Chem. Phys.
95
,
4715
(
1991
).
71.
E. F.
Caldin
,
J. E.
Crooks
,
D.
O’Donnell
,
D.
Smith
, and
S.
Toner
,
Chem. Soc. J. Faraday Trans. 1
68
,
849
(
1972
).
72.
G. W.
Robinson
and
R. P.
Frosch
,
J. Chem. Phys.
38
,
1187
(
1963
).
73.
(a)
S. K.
Doom
,
P. O.
Stoutland
,
R. B.
Dyer
, and
W. H.
Woodruff
,
J. Am. Chem. Soc.
114
,
3133
(
1992
);
(b)
S. K.
Doom
,
R. B.
Dyer
,
P. O.
Stoutland
, and
W. H.
Woodruff
,
J. Am. Chem. Soc.
115
,
6398
(
1993
).,
J. Am. Chem. Soc.
74.
S. K.
Doom
and
J. T.
Hupp
,
J. Am. Chem. Soc.
111
,
1142
(
1989
).
75.
I. R.
Gould
,
R. H.
Young
,
R. E.
Moody
, and
S.
Farid
,
J. Phys. Chem.
95
,
2068
(
1991
).
76.
J. D.
Simon
,
Acc. Chem. Res.
21
,
128
(
1988
).
77.
E. W.
Castner
,
M.
Maroncelli
, and
G. R.
Fleming
,
J. Chem. Phys.
86
,
1090
(
1987
).
78.
C. Reichardt, Solvent Effects in Organic Chemistry (Chemie, Weinheim, 1979);
2nd ed., idem. (Chemie, Weinheim, 1988).
79.
Handbook of Chemistry and Physics, 57th ed. (CRC, Boca Raton, 1977).
80.
E.
Ikada
and
J.
Watanabe
,
J. Phys. Chem.
78
,
1078
(
1974
).
81.
M.
Maroncelli
,
J.
McInnis
, and
G. R.
Fleming
,
Science
243
,
1674
(
1989
).
82.
N. E. Hill, W. E. Vaughan, A. H. Price, and M. Davies, Dielectric Properties and Molecular Behaviour (Van Nostrand, London, 1969).
83.
Merck Index, 10th ed. (Merck, New York, 1983). For butyronitrile index.
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