Vibrational energy transfer (VET) between two isotopologues of [Re(dcb)(CO)3Br] immobilized on a TiO2 surface is studied with the help of 2D IR spectroscopy in dependence of surface coverage. To dilute the molecules on the surface, and thereby control the intermolecular distances, two different diluents have been used: a third isotopologue of the same molecule and 4-cyanobenzoic acid. As expected, the VET rate decreases with dilution. For a quantitative investigation of the distance dependence of the VET rate, we analyze the data based on an excitonic model. This model reveals the typical 1/r6-distance dependence for a dimer of a donor and acceptor, similar to the nuclear Overhauser effect in NMR spectroscopy or Förster resonant energy transfer in electronic spectroscopy. However, VET becomes a collective phenomenon on the surface, with the existence of a network of coupled molecules and its disappearance below a percolation threshold, dominating the concentration dependence of the VET rate.

1.
R.
Van Grondelle
and
V. I.
Novoderezhkin
,
Phys. Chem. Chem. Phys.
8
,
793
(
2006
).
2.
L.
Stryer
and
R. P.
Haugland
,
Proc. Natl. Acad. Sci. U. S. A.
58
,
719
(
1967
).
3.
R. A.
Bell
and
J. K.
Saunders
,
Can. J. Chem.
48
,
1114
(
1970
).
4.
R. E.
Schirmer
,
J. H.
Noggle
,
J. P.
Davis
, and
P. A.
Hart
,
J. Am. Chem. Soc.
92
,
3266
(
1970
).
5.
H.
Bian
,
H.
Chen
,
J.
Li
,
X.
Wen
, and
J.
Zheng
,
J. Phys. Chem. A
115
,
11657
(
2011
).
6.
H.
Bian
,
X.
Wen
,
J.
Li
,
H.
Chen
,
S.
Han
,
X.
Sun
,
J.
Song
,
W.
Zhuang
, and
J.
Zheng
,
Proc. Natl. Acad. Sci. U. S. A.
108
,
4737
(
2011
).
7.
J.
Li
,
H.
Bian
,
X.
Wen
,
H.
Chen
,
K.
Yuan
, and
J.
Zheng
,
J. Phys. Chem. B
116
,
12284
(
2012
).
8.
H.
Bian
,
J.
Li
,
Q.
Zhang
,
H.
Chen
,
W.
Zhuang
,
Y. Q.
Gao
, and
J.
Zheng
,
J. Phys. Chem. B
116
,
14426
(
2012
).
9.
J.
Li
,
H.
Bian
,
H.
Chen
,
X.
Wen
,
B. T.
Hoang
, and
J.
Zheng
,
J. Phys. Chem. B
117
,
4274
(
2013
).
10.
H.
Chen
,
X.
Wen
,
J.
Li
, and
J.
Zheng
,
J. Phys. Chem. A
118
,
2463
(
2014
).
11.
H.
Chen
,
X.
Wen
,
X.
Guo
, and
J.
Zheng
,
Phys. Chem. Chem. Phys.
16
,
13995
(
2014
).
12.
H.
Chen
,
H.
Bian
,
J.
Li
,
X.
Wen
,
Q.
Zhang
,
W.
Zhuang
, and
J.
Zheng
,
J. Phys. Chem. B
119
,
4333
(
2015
).
13.
J. P.
Kraack
,
A.
Frei
,
R.
Alberto
, and
P.
Hamm
,
J. Phys. Chem. Lett.
8
,
2489
(
2017
).
14.
J. P.
Kraack
and
P.
Hamm
,
J. Phys. Chem. C
122
,
2259
(
2018
).
15.
J. P.
Kraack
,
L.
Sévery
,
S. D.
Tilley
, and
P.
Hamm
,
J. Phys. Chem. Lett.
9
,
49
(
2018
).
16.
S.
Zhang
,
M.
Li
,
W.
Qiu
,
J.
Han
,
H.
Wang
, and
X.
Liu
,
Appl. Catal., B
259
,
118113
(
2019
).
17.
C. D.
Windle
,
E.
Pastor
,
A.
Reynal
,
A. C.
Whitwood
,
Y.
Vaynzof
,
J. R.
Durrant
,
R. N.
Perutz
, and
E.
Reisner
,
Chem. - Eur. J.
21
,
3746
(
2015
).
18.
M.
Abdellah
,
A. M.
El-Zohry
,
L. J.
Antila
,
C. D.
Windle
,
E.
Reisner
, and
L.
Hammarström
,
J. Am. Chem. Soc.
139
,
1226
(
2017
).
19.
J.
Huang
,
M. G.
Gatty
,
B.
Xu
,
P. B.
Pati
,
A. S.
Etman
,
L.
Tian
,
J.
Sun
,
L.
Hammarström
, and
H.
Tian
,
Dalton Trans.
47
,
10775
(
2018
).
20.
M.
Waki
,
K. I.
Yamanaka
,
S.
Shirai
,
Y.
Maegawa
,
Y.
Goto
,
Y.
Yamada
, and
S.
Inagaki
,
Chem. - Eur. J.
24
,
3846
(
2018
).
21.
L.
Price
,
Energy Procedia
151
,
120
128
(
2018
).
22.
G.
Sahara
and
O.
Ishitani
,
Inorg. Chem.
54
,
5096
(
2015
).
23.
K.
Oppelt
,
R.
Fernández-Terán
,
R.
Pfister
, and
P.
Hamm
,
J. Phys. Chem. C
123
,
19952
(
2019
).
24.
K.
Oppelt
,
M.
Mosberger
,
J.
Ruf
,
R.
Fernández-Terán
,
B.
Probst
,
R.
Alberto
, and
P.
Hamm
,
J. Phys. Chem. C
124
,
12502
(
2020
).
25.
N.
Weder
,
B.
Probst
,
L.
Sévery
,
R. J.
Fernández-Terán
,
J.
Beckord
,
O.
Blacque
,
S. D.
Tilley
,
P.
Hamm
,
J.
Osterwalder
, and
R.
Alberto
,
Catal. Sci. Technol.
10
,
2549
(
2020
).
26.
R.
Alberto
,
A.
Egli
,
U.
Abram
,
K.
Hegetschweiler
,
V.
Gramlich
, and
P. A.
Schubiger
,
J. Chem. Soc., Dalton Trans.
1994
,
2815
.
27.
J. M.
Smieja
and
C. P.
Kubiak
,
Inorg. Chem.
49
,
9283
(
2010
).
28.
J. P.
Kraack
,
D.
Lotti
, and
P.
Hamm
,
J. Phys. Chem. Lett.
5
,
2325
(
2014
).
29.
P.
Hamm
,
M.
Lim
, and
R. M.
Hochstrasser
,
J. Chem. Phys.
107
,
10523
(
1997
).
30.
P.
Hamm
,
R. A.
Kaindl
, and
J.
Stenger
,
Opt. Lett.
25
,
1798
(
2000
).
31.
J.
Helbing
and
P.
Hamm
,
J. Opt. Soc. Am. B
28
,
171
(
2011
).
32.
R.
Bloem
,
S.
Garrett-Roe
,
H.
Strzalka
,
P.
Hamm
, and
P.
Donaldson
,
Opt. Express
18
,
27067
(
2010
).
33.
K.
Kwak
,
J.
Zheng
,
H.
Cang
, and
M. D.
Fayer
,
J. Phys. Chem. B
110
,
19998
(
2006
).
34.
Q.
Guo
,
P.
Pagano
,
Y.-L.
Li
,
A.
Kohen
, and
C. M.
Cheatum
,
J. Chem. Phys.
142
,
212427
(
2015
).
35.
T. L. C.
Jansen
and
J.
Knoester
,
J. Phys. Chem. B
110
,
22910
(
2006
).
36.
P.
Hamm
and
M.
Zanni
,
Concepts and Methods of 2D Infrared Spectroscopy
(
Cambridge University Press
,
Cambridge
,
2011
).
37.
N. G.
Van Kampen
,
Stochastic Processes in Physics and Chemistry
(
Elsevier
,
Amsterdam
,
1992
).
38.
C.
Liang
and
T. L.
Jansen
,
J. Chem. Theory Comput.
8
,
1706
(
2012
).
39.
C. L.
Anfuso
,
R. C.
Snoeberger
,
A. M.
Ricks
,
W.
Liu
,
D.
Xiao
,
V. S.
Batista
, and
T.
Lian
,
J. Am. Chem. Soc.
133
,
6922
(
2011
).
40.
C. L.
Anfuso
,
D.
Xiao
,
A. M.
Ricks
,
C. F.
Negre
,
V. S.
Batista
, and
T.
Lian
,
J. Phys. Chem. C
116
,
24107
(
2012
).
41.
A.
Ge
,
B.
Rudshteyn
,
B. T.
Psciuk
,
D.
Xiao
,
J.
Song
,
C. L.
Anfuso
,
A. M.
Ricks
,
V. S.
Batista
, and
T.
Lian
,
J. Phys. Chem. C
120
,
20970
(
2016
).
42.
H.
Vanselous
,
P. E.
Videla
,
V. S.
Batista
, and
P. B.
Petersen
,
J. Phys. Chem. C
122
,
26018
(
2018
).
43.
M.
Grechko
and
M. T.
Zanni
,
J. Chem. Phys.
137
,
184202
(
2012
).
44.
C. L.
Anfuso
,
A. M.
Ricks
,
W.
Rodríguez-Córdoba
, and
T.
Lian
,
J. Phys. Chem. C
116
,
26377
(
2012
).
45.
J.
Nishida
,
C.
Yan
, and
M. D.
Fayer
,
J. Chem. Phys.
146
,
094201
(
2017
).
46.
M.
Delor
,
S. A.
Archer
,
T.
Keane
,
A. J.
Meijer
,
I. V.
Sazanovich
,
G. M.
Greetham
,
M.
Towrie
, and
J. A.
Weinstein
,
Nat. Chem.
9
,
1099
(
2017
).
47.
D. E.
Rosenfeld
,
Z.
Gengeliczki
,
B. J.
Smith
,
T. D. P.
Stack
, and
M. D.
Fayer
,
Science
334
,
634
(
2011
).
48.
T.
Higashi
and
K.
Osaki
,
Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.
37
,
777
(
1981
).
49.
M.
Sahini
and
M.
Sahimi
,
Applications of Percolation Theory
(
CRC Press
,
Boca Raton
,
1994
).
50.
H.
Tal-Ezer
and
R.
Kosloff
,
J. Chem. Phys.
81
,
3967
(
1984
).

Supplementary Material

You do not currently have access to this content.