We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cistrans- and transcis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work).

1.
W. R.
Browne
and
B. L.
Feringa
,
Nat. Nanotechnol.
1
,
25
(
2006
).
2.
Y.
Shirai
,
J. F.
Morin
,
T.
Sasaki
,
J. M.
Guerrero
, and
J. M.
Tour
,
Chem. Soc. Rev.
35
,
1043
(
2006
).
3.
E. R.
Kay
,
D. A.
Leigh
, and
F.
Zerbetto
,
Angew. Chem. Int. Ed.
46
,
72
(
2007
).
4.
V.
Balzani
,
A.
Credi
, and
M.
Venturi
,
Chem. Soc. Rev.
38
,
1542
(
2009
).
5.
A.
Coskun
,
M.
Banaszak
,
R. D.
Astumian
,
J. F.
Stoddart
, and
B. A.
Grzybowski
,
Chem. Soc. Rev.
41
,
19
(
2012
).
6.
T.
Muraoka
and
K.
Kinbara
,
J. Photochem. Photobiol. C
13
,
136
(
2012
).
7.
T.
Raeker
,
N. O.
Carstensen
, and
B.
Hartke
,
J. Phys. Chem. A
116
,
11241
(
2012
).
8.
H. M. D.
Bandara
and
S. C.
Burdette
,
Chem. Soc. Rev.
41
,
1809
(
2012
).
9.
A. A.
Beharry
and
G. A.
Woolley
,
Chem. Soc. Rev.
40
,
4422
(
2011
).
10.
C. J.
Barrett
,
J. I.
Mamiya
,
K. G.
Yager
, and
T.
Ikeda
,
Soft Matter
3
,
1249
(
2007
).
11.
T.
Schultz
,
J.
Quenneville
,
B.
Levine
,
A.
Toniolo
,
T.
Martinez
,
S.
Lochbrunner
,
M.
Schmitt
,
J.
Shaffer
,
M.
Zgierski
, and
A.
Stolow
,
J. Am. Chem. Soc.
125
,
8098
(
2003
).
12.
C.
Ciminelli
,
G.
Granucci
, and
M.
Persico
,
Chem.-Eur. J.
10
,
2327
(
2004
).
13.
A.
Toniolo
,
C.
Ciminelli
,
M.
Persico
, and
T. J.
Martínez
,
J. Chem. Phys.
123
,
234308
(
2005
).
14.
M.
Böckmann
,
N. L.
Doltsinis
, and
D.
Marx
,
Phys. Rev. E
78
,
036101
(
2008
).
15.
M.
Böckmann
,
N. L.
Doltsinis
, and
D.
Marx
,
J. Phys. Chem. A
114
,
745
(
2010
).
16.
O.
Weingart
,
Z.
Lan
,
A.
Koslowski
, and
W.
Thiel
,
J. Phys. Chem. Lett.
2
,
1506
(
2011
).
17.
J. A.
Gamez
,
O.
Weingart
,
A.
Koslowski
, and
W.
Thiel
,
J. Chem. Theory Comput.
8
,
2352
(
2012
).
18.
G.
Tiberio
,
L.
Muccioli
,
R.
Berardi
, and
C.
Zannoni
,
ChemPhysChem
11
,
1018
(
2010
).
19.
P.
Duchstein
,
C.
Neiss
,
A.
Görling
, and
D.
Zahn
,
J. Mol. Model.
18
,
2479
(
2012
).
20.
P. H.
Nguyen
and
G.
Stock
,
Chem. Phys.
323
,
36
(
2006
).
21.
H.
Heinz
,
R. A.
Vaia
,
H.
Koerner
, and
B. L.
Farmer
,
Chem. Mater.
20
,
6444
(
2008
).
22.
V.
Teboul
,
M.
Saiddine
,
J.-M.
Nunzi
, and
J.-B.
Accary
,
J. Chem. Phys.
134
,
114517
(
2011
).
23.
A.
Warshel
and
R. M.
Weiss
,
J. Am. Chem. Soc.
102
,
6218
(
1980
).
24.
J.
Åqvist
and
A.
Warshel
,
Chem. Rev.
93
,
2523
(
1993
).
25.
Y.-T.
Chang
and
W. H.
Miller
,
J. Phys. Chem.
94
,
5884
(
1990
).
26.
F.
Bernardi
,
M.
Olivucci
, and
M. A.
Robb
,
J. Am. Chem. Soc.
114
,
1606
(
1992
).
27.
R.
Valero
,
L.
Song
,
J.
Gao
, and
D. G.
Truhlar
,
J. Chem. Theory Comput.
5
,
1
(
2009
).
28.
S. C. L.
Kamerlin
and
A.
Warshel
,
Faraday Discuss.
145
,
71
(
2010
).
29.
S. C. L.
Kamerlin
,
J.
Cao
,
E.
Rosta
, and
A.
Warshel
,
J. Phys. Chem. B
113
,
10905
(
2009
).
30.
D. W.
Brenner
,
Phys. Rev. B
42
,
9458
(
1990
);
D. W.
Brenner
,
Phys. Rev. B
46
,
1948
(
1992
).
31.
B. C.
Bolding
and
H. C.
Andersen
,
Phys. Rev. B
41
,
10568
(
1990
).
32.
A. C. T.
van Duin
,
S.
Dasgupta
,
F.
Lorant
, and
W. A.
Goddard
,
J. Phys. Chem. A
105
,
9396
(
2001
).
33.
A. C. T.
van Duin
,
A.
Strachan
,
S.
Stewman
,
Q.
Zhang
, and
W. A.
Goddard
,
J. Phys. Chem. A
107
,
3803
(
2003
).
34.
S. S.
Han
,
J. K.
Kang
,
H. M.
Lee
,
A. C. T.
van Duin
, and
W. A.
Goddard
,
J. Chem. Phys.
123
,
114704
(
2005
).
35.
K.
Chenoweth
,
A. C. T.
van Duin
, and
W. A.
Goddard
,
J. Phys. Chem. A
112
,
1040
(
2008
).
36.
A.
Strachan
,
E.
Kober
,
A. C. T.
van Duin
,
J.
Oxgaard
, and
W. A.
Goddard
,
J. Chem. Phys.
122
,
054502
(
2005
).
37.
O.
Rahaman
,
A. C. T.
van Duin
,
W. A.
Goddard
, and
D. J.
Doren
,
J. Phys. Chem. B
115
,
249
(
2011
).
38.
K. D.
Nielson
,
A. C. T.
van Duin
,
J.
Oxgaard
,
W.
Deng
, and
W. A.
Goddard
,
J. Phys. Chem. A
109
,
493
(
2005
).
39.
T.
Ishikawa
and
T.
Noro
,
J. Chem. Phys.
115
,
7503
(
2001
).
40.
H. R.
Larsson
,
A. C. T.
van Duin
, and
B.
Hartke
,
J. Comput. Chem.
34
,
2178
(
2013
).
41.
See supplementary material at http://dx.doi.org/10.1063/1.4837237 for more details on the GA algorithm and settings, for further fitting results not shown in Sec. III A, and for additional data on determining the parameters in Eq. (1).
42.
G.
Granucci
,
M.
Persico
, and
A.
Toniolo
,
J. Chem. Phys.
114
,
10608
(
2001
).
43.
C.
Ciminelli
,
G.
Granucci
, and
M.
Persico
,
J. Chem. Phys.
123
,
174317
(
2005
).
44.
C.
Ciminelli
,
G.
Granucci
, and
M.
Persico
,
Chem. Phys.
349
,
325
(
2008
).
45.
O.
Carstensen
,
J.
Sielk
,
J.
Schönborn
,
G.
Granucci
, and
B.
Hartke
,
J. Chem. Phys.
133
,
124305
(
2010
).
46.
Photoselective Chemistry, Part I
, edited by
J.
Jortner
and
R. D.
Levine
(
Wiley
,
New York
,
1981
), Vol.
47
.
47.
C. W.
Eaker
,
J. Chem. Phys.
87
,
4532
(
1987
).
48.
R.
Englman
and
J.
Jortner
,
Mol. Phys.
18
,
145
(
1970
).
49.
N.
Kitamura
,
N.
Sakata
,
H. B.
Kim
, and
S.
Habuchi
,
Anal. Sci.
15
,
413
(
1999
).
50.
F.
Ehlers
,
D. A.
Wild
,
T.
Lenzer
, and
K.
Oum
,
J. Phys. Chem. A
111
,
2257
(
2007
).
51.
S.
Hayashi
,
E.
Tajkhorshid
, and
K.
Schulten
,
Biophys. J.
96
,
403
(
2009
).
52.
H.
Rau
, “
Photochromism
,” in
Molecules and Systems
, edited by
H.
Durr
and
H.
Bouas-Laurent
(
Elsevier
,
Amsterdam
,
1990
), Chap. 4, p.
165
.
53.
A.
Mostad
and
C.
Romming
,
Acta Chem. Scand.
25
,
3561
(
1971
).
54.
J. A.
Bouwstra
,
A.
Schouten
, and
J.
Kroon
,
Acta Crystallogr. C
C39
,
1121
(
1983
).
55.
T.
Cusati
,
G.
Granucci
,
E.
Martínez-Núñez
,
F.
Martini
,
M.
Persico
, and
S.
Vázquez
,
J. Phys. Chem. A
116
,
98
(
2012
).
56.
L.
Gagliardi
,
G.
Orlandi
,
F.
Bernardi
,
A.
Cembran
, and
M.
Garavelli
,
Theor. Chem. Acc.
111
,
363
(
2004
).
57.
A.
Cembran
,
F.
Bernardi
,
M.
Garavelli
,
L.
Gagliardi
, and
G.
Orlandi
,
J. Am. Chem. Soc.
126
,
3234
(
2004
).
58.
T.
Pancur
,
F.
Renth
,
F.
Temps
,
B.
Harbaum
,
A.
Krüger
,
R.
Herges
, and
C.
Näther
,
Phys. Chem. Chem. Phys.
7
,
1985
(
2005
).

Supplementary Material

You do not currently have access to this content.