Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm−1 blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 11 (band I) and 11ππ (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm−1), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to varying solvation dynamics. This will have implications for ultrafast processes associated with electron-transfer, charge transfer, and also the photophysical aspects of excited states.

1.
J. D.
Reinheimer
,
J. D.
Harley
, and
W. W.
Meyers
,
J. Org. Chem.
28
,
1575
(
1963
).
2.
C.
Reichardt
,
Angew. Chem., Int. Ed.
4
,
29
(
1965
);
C.
Reichardt
,
Pure Appl. Chem.
54
,
1867
(
1982
).
3.
O.
Acevedo
and
W. L.
Jorgensen
,
J. Phys. Chem. B
114
,
8425
(
2010
).
4.
C.
Reichardt
,
Solvents and Solvent Effects in Organic Chemistry
(
Wiley-VCH Verlag GmBH & Co.
,
Weinheim
,
2011
).
5.
D. G.
Truhlar
,
Nat. Chem.
5
,
902
(
2013
);
[PubMed]
S. J.
Klippenstein
,
V. S.
Pande
, and
D. G.
Truhlar
,
J. Am. Chem. Soc.
136
,
528
(
2014
).
[PubMed]
6.
S.
Ha
,
J.
Gao
,
B.
Tidor
,
J. W.
Brady
, and
M.
Karplus
,
J. Am. Chem. Soc.
113
,
1553
(
1991
).
7.
M. W.
Wong
,
K. B.
Wiberg
, and
M. J.
Frisch
,
J. Am. Chem. Soc.
114
,
1645
(
1992
).
8.
J. M.
Hicks
,
M. T.
Vandersall
,
E. V.
Sitzmann
, and
K. B.
Eisenthal
,
Chem. Phys. Lett.
135
,
413
(
1987
).
9.
E.
Vauthey
,
D.
Phillips
, and
A. W.
Parker
,
J. Phys. Chem.
96
,
7356
(
1992
);
E.
Vauthey
,
A. W.
Parker
,
B.
Nohova
, and
D.
Phillips
,
J. Am. Chem. Soc.
116
,
9182
(
1994
);
M.
Koch
,
G.
Licari
, and
E.
Vauthey
,
J. Phys. Chem. B
119
,
11846
(
2015
).
[PubMed]
10.
H.
Heitele
,
Angew. Chem., Int. Ed.
32
,
359
(
1993
).
11.
P.
Chen
and
T. J.
Meyer
,
Chem. Rev.
98
,
1439
(
1998
).
12.
N.
Biswas
and
S.
Umapathy
,
Chem. Phys. Lett.
294
,
181
(
1998
);
N.
Biswas
and
S.
Umapathy
,
J. Raman Spectrosc.
32
,
471
(
2001
);
N.
Biswas
and
S.
Umapathy
,
J. Chem. Phys.
118
,
5526
(
2003
).
13.
J. C.
Scaiano
,
J. Am. Chem. Soc.
102
,
7747
(
1980
);
A.
Rosspeintner
,
B.
Lang
, and
E.
Vauthey
,
Annu. Rev. Phys. Chem.
64
,
247
(
2013
).
[PubMed]
14.
V. R.
Kumar
,
N.
Rajkumar
, and
S.
Umapathy
,
J. Chem. Phys.
142
,
024305
(
2015
).
15.
V. R.
Kumar
,
N.
Rajkumar
,
F.
Ariese
, and
S.
Umapathy
,
J. Phys. Chem. A
119
,
10147
(
2015
).
16.
G.
Balakrishnan
,
S. K.
Sahoo
,
B. K.
Chowdhury
, and
S.
Umapathy
,
Faraday Discuss.
145
,
443
(
2010
).
17.
T.
Lai
,
B. T.
Lim
, and
E. C.
Lim
,
J. Am. Chem. Soc.
104
,
7631
(
1982
);
E. C.
Lim
,
J. Phys. Chem.
90
,
6770
(
1986
).
18.
B.
Heinz
,
B.
Schmidt
,
C.
Root
,
H.
Satzger
,
F.
Milota
,
B.
Fierz
,
T.
Kiefhaber
,
W.
Zinth
, and
P.
Gilch
,
Phys. Chem. Chem. Phys.
8
,
3432
(
2006
);
[PubMed]
T.
Villnow
,
G.
Ryseck
,
V.
Rai-Constapel
,
C. M.
Marian
, and
P.
Gilch
,
J. Phys. Chem. A
118
,
11696
(
2014
).
[PubMed]
19.
W.
Liptay
,
Angew. Chem., Int. Ed.
8
,
177
(
1969
).
20.
E.
Arunan
,
G. R.
Desiraju
,
R. A.
Klein
,
J.
Sadlej
,
S.
Scheiner
,
I.
Alkorta
,
D. C.
Clary
,
R. H.
Crabtree
,
J. J.
Dannenberg
,
P.
Hobza
,
H. G.
Kjaergaard
,
A. C.
Legon
,
B.
Mennuci
, and
D. J.
Nesbitt
,
Pure Appl. Chem.
83
,
1637
(
2011
).
21.
T. S.
Moore
and
T. F.
Winmill
,
J. Chem. Soc., Trans.
101
,
1635
(
1912
);
W. M.
Latimer
and
W. H.
Rodebush
,
J. Am. Chem. Soc.
42
,
1419
(
1920
);
M. L.
Huggins
,
Phys. Rev.
18
,
313
(
1921
);
M. L.
Huggins
,
Phys. Rev.
19
,
346
(
1922
);
J.
Lennard-Jones
and
J. A.
Pople
,
Proc. R. Soc. A
205
,
155
(
1951
);
M. L.
Huggins
,
Angew. Chem., Int. Ed.
10
,
147
(
1971
).
22.
J.
Sponer
,
J.
Leszczynski
, and
P.
Hobza
,
J. Biomol. Struct. Dyn.
14
,
117
(
1996
);
[PubMed]
J.
Waluk
,
Acc. Chem. Res.
36
,
832
(
2003
);
[PubMed]
T.
Seki
,
S.
Yagai
,
T.
Karatsu
, and
A.
Kitamura
,
J. Org. Chem.
73
,
3328
(
2008
);
[PubMed]
L. R.
MacGillivray
,
J. Org. Chem.
73
,
3311
(
2008
);
[PubMed]
Y. S.
Kim
and
R.
Hochstrasser
,
J. Phys. Chem. B
113
,
8231
(
2009
);
[PubMed]
G.
Cui
,
Z.
Lan
, and
W.
Thiel
,
J. Am. Chem. Soc.
134
,
1662
(
2012
);
[PubMed]
J.
Saveant
and
C.
Tard
,
J. Am. Chem. Soc.
136
,
8907
(
2014
);
[PubMed]
T.
Aida
,
E. W.
Meijer
, and
S. I.
Stupp
,
Science
335
,
813
(
2012
);
[PubMed]
A. G.
Slater
,
L. M. A.
Perdigao
,
P. H.
Beton
, and
N. R.
Champness
,
Acc. Chem. Res.
47
,
3417
(
2014
).
[PubMed]
23.
G. J.
Zhao
and
K.
Han
,
Acc. Chem. Res.
45
,
404
(
2012
);
[PubMed]
K. L.
Han
and
G. J.
Zhao
,
Hydrogen Bonding and Transfer in the Excited State
(
John Wiley & Sons Ltd.
,
Chichester
,
2011
).
24.
F. A. S.
Chipem
,
A.
Mishra
, and
G.
Krishnamoorthy
,
Phys. Chem. Chem. Phys.
14
,
8775
(
2012
);
[PubMed]
E. M. M.
Tan
,
M.
Hilbers
, and
W. J.
Buma
,
J. Phys. Chem. Lett.
5
,
2464
(
2014
);
[PubMed]
Y.
Yang
,
L.
Liu
,
J.
Chen
, and
K.
Han
,
Phys. Chem. Chem. Phys.
16
,
17828
(
2014
).
[PubMed]
25.
P.
Suppan
,
J. Photochem. Photobiol., A
50
,
293
(
1990
).
26.
E.
Buncel
and
S.
Rajagopal
,
Acc. Chem. Res.
23
,
226
(
1990
);
C.
Reichardt
,
Chem. Rev.
94
,
2319
(
1994
);
M. J.
Kamlet
,
J. M.
Abboud
,
M. H.
Abraham
, and
R. W.
Taft
,
J. Org. Chem.
48
,
2877
(
1983
).
27.
Y.
Marcus
,
Chem. Soc. Rev.
22
,
409
(
1993
).
28.
J.
Choi
and
M.
Cho
,
J. Chem. Phys.
134
,
154513
(
2011
);
[PubMed]
C. J.
Huber
,
T. C.
Anglin
,
B. H.
Jones
,
N.
Muthu
,
C. J.
Cramer
, and
A. M.
Massari
,
J. Phys. Chem. A
116
,
9279
(
2012
).
[PubMed]
29.
G.
Balakrishnan
,
P.
Mohandas
, and
S.
Umapathy
,
J. Phys. Chem. A
105
,
7778
(
2001
);
B.
Abel
,
U.
Buck
,
A. L.
Sobolewski
, and
W.
Domcke
,
Phys. Chem. Chem. Phys.
14
,
22
(
2012
);
[PubMed]
S.
Lobsiger
,
S.
Blaser
,
R. K.
Sinha
,
H.
Frey
, and
S.
Leutwyler
,
Nat. Chem.
6
,
989
(
2014
).
[PubMed]
30.
A.
Domingo
,
A.
Rodriguez-Fortea
, and
C.
Graaf
,
J. Chem. Theory Comput.
8
,
235
(
2012
).
31.
L.
Onsager
,
J. Am. Chem. Soc.
58
,
1486
(
1936
);
J. G.
Kirkwood
,
J. Chem. Phys.
7
,
911
(
1939
).
32.
J.
Tomasi
and
M.
Persico
,
Chem. Rev.
94
,
2027
(
1994
);
V.
Barone
and
M.
Cossi
,
J. Phys. Chem. A
102
,
1995
(
1998
);
C. J.
Cramer
and
D. G.
Truhlar
,
Chem. Rev.
99
,
2161
(
1999
);
[PubMed]
J.
Tomasi
,
B.
Mennucci
, and
R.
Cammi
,
Chem. Rev.
105
,
2999
(
2005
);
[PubMed]
B.
Mennucci
,
J.
Tomasi
,
R.
Cammi
,
J. R.
Cheeseman
,
M. J.
Frisch
,
F. J.
Devlin
,
S.
Gabriel
, and
P. J.
Stephens
,
J. Phys. Chem. A
106
,
6102
(
2002
).
33.
E. S.
Marcos
,
B.
Terryn
, and
J.
Rivail
,
J. Phys. Chem.
89
,
4695
(
1985
);
M. M.
Karelson
and
M. C.
Zerner
,
J. Phys. Chem.
96
,
6949
(
1992
);
I.
Tunon
,
D.
Rinaldi
,
M. F.
Ruiz-Lopez
, and
J. L.
Rivail
,
J. Phys. Chem.
99
,
3798
(
1995
).
34.
H. M.
Sevian
and
J. L.
Skinner
,
Theor. Chim. Acta
82
,
29
(
1992
).
35.
K.
Coutinho
and
S.
Canuto
,
J. Mol. Struct.: THEOCHEM
632
,
235
(
2003
).
36.
M. P.
Allen
and
D. J.
Tildesley
,
Computer Simulation of Liquids
(
Clarendon Press
,
Oxford
,
1987
);
P. A.
Kollman
,
Acc. Chem. Res.
29
,
461
(
1996
);
M.
Karplus
and
J. A.
Mccammon
,
Nat. Struct. Biol.
9
,
646
(
2002
);
[PubMed]
S.
Urahata
and
S.
Canuto
,
Int. J. Quantum Chem.
80
,
1062
(
2000
);
A. V.
Marenich
,
C. J.
Cramer
, and
D. G.
Truhlar
,
J. Phys. Chem. B
119
,
958
(
2015
);
[PubMed]
K. H.
Hopmann
,
K.
Ruud
,
M.
Pecul
,
A.
Kudelski
,
M.
Dracinsky
, and
P.
Bour
,
J. Phys. Chem. B
115
,
4128
(
2011
);
[PubMed]
J.
Kaminsky
,
P.
Bour
, and
J.
Kubelka
,
J. Phys. Chem. A
115
,
30
(
2011
);
[PubMed]
J.
Kaminsky
,
J.
Sebek
, and
P.
Bour
,
J. Comput. Chem.
30
,
983
(
2009
);
[PubMed]
P.
Stepanek
and
P.
Bour
,
Phys. Chem. Chem. Phys.
16
,
20639
(
2014
);
[PubMed]
J. R.
Cheeseman
,
M. S.
Shaik
,
P. L. A.
Popelier
, and
E. W.
Blanch
,
J. Am. Chem. Soc.
133
,
4991
(
2011
);
[PubMed]
S. T.
Mutter
,
F.
Zielinski
,
J. R.
Cheeseman
,
C.
Johannessen
,
P. L. A.
Popelier
, and
E. W.
Blanch
,
Phys. Chem. Chem. Phys.
17
,
6016
(
2015
);
[PubMed]
T.
Schwabe
,
J. Phys. Chem. B
119
,
10693
(
2015
).
[PubMed]
37.
R. S.
Larsen
,
W. L.
Glover
, and
B. J.
Schwartz
,
Science
329
,
65
(
2010
);
[PubMed]
E.
Guardia
,
I.
Skarmoustsos
, and
M.
Masia
,
J. Phys. Chem. B
119
,
8926
(
2015
);
[PubMed]
K.
Usui
,
J.
Hunger
,
M.
Sulpiz
,
T.
Ohto
,
M.
Bonn
, and
Y.
Nagata
,
J. Phys. Chem. B
119
,
10597
(
2015
);
[PubMed]
I. W.
Kuo
and
C. J.
Mundy
,
Science
303
,
658
(
2004
);
[PubMed]
A. K.
Tummanapelli
and
S.
Vasudevan
,
Phys. Chem. Chem. Phys.
17
,
6383
(
2015
);
[PubMed]
N. K.
Jena
,
I.
Josefsson
,
S. K.
Eriksson
,
A.
Hagfeldt
,
H.
Siegbahn
,
O.
Bjorneholm
,
H.
Rensmo
, and
M.
Odelius
,
Chem. Eur. J.
21
,
4049
(
2015
);
M.
Eichinger
,
P.
Tavan
,
J.
Hutler
, and
M.
Parrinello
,
J. Chem. Phys.
110
,
10452
(
1999
);
J.
Gao
,
Acc. Chem. Res.
29
,
298
(
1996
);
D.
Bakowies
and
W.
Thiel
,
J. Phys. Chem.
100
,
10580
(
1996
);
H. M.
Senn
and
W.
Thiel
,
Angew. Chem., Int. Ed.
48
,
1198
(
2009
);
P.
Diamantis
,
J. F.
Gonthier
,
I.
Tavernelli
, and
U.
Rothlisberger
,
J. Phys. Chem. B
118
,
3950
(
2014
);
[PubMed]
B.
Mennucci
,
Phys. Chem. Chem. Phys.
15
,
6583
(
2013
);
[PubMed]
H.
Ma
and
Y.
Ma
,
J. Chem. Phys.
138
,
224505
(
2013
);
[PubMed]
C.
Bistafa
and
S.
Canuto
,
Theor. Chem. Acc.
132
,
1299
(
2013
);
H.
Lin
and
D. G.
Truhlar
,
Theor. Chem. Acc.
117
,
185
(
2007
).
38.
J.
Catalan
and
J. P.
Catalan
,
Phys. Chem. Chem. Phys.
13
,
4072
(
2011
);
[PubMed]
O. W.
Kolling
,
J. Phys. Chem.
96
,
6217
(
1992
);
R. A.
Nyquist
,
Appl. Spectrosc.
44
,
433
(
1990
);
S. E.
DeBolt
and
P. A.
Kollman
,
J. Am. Chem. Soc.
112
,
7515
(
1990
);
B.
Fang
,
T.
Wang
,
X.
Chen
,
T.
Jin
,
R.
Zhang
, and
W.
Zhuang
,
J. Phys. Chem. B
119
,
12390
(
2015
).
[PubMed]
39.
N. A.
Besley
,
J. Phys. Chem. A
108
,
10794
(
2004
);
M. F.
DeCamp
,
L.
DeFlores
,
J. M.
McCracken
,
A.
Tokmakoff
,
K.
Kwac
, and
M.
Cho
,
J. Phys. Chem. B
109
,
11016
(
2005
);
[PubMed]
M.
Cho
,
Chem. Rev.
108
,
1331
(
2008
);
[PubMed]
J.
Jeon
,
S.
Yang
,
J.
Choi
, and
M.
Cho
,
Acc. Chem. Res.
42
,
1280
(
2009
);
[PubMed]
K.
Kwac
and
M.
Cho
,
J. Chem. Phys.
119
,
2247
(
2003
);
B.
Blasiak
and
M.
Cho
,
J. Chem. Phys.
140
,
164107
(
2014
);
[PubMed]
B.
Blasiak
and
M.
Cho
,
J. Chem. Phys.
143
,
164111
(
2015
);
[PubMed]
H.
Torii
,
J. Phys. Chem. Lett.
6
,
727
(
2015
).
[PubMed]
40.
A.
Beckett
and
G.
Porter
,
Trans. Faraday Soc.
59
,
2038
(
1963
);
A.
Beckett
and
G.
Porter
,
Trans. Faraday Soc.
59
,
2051
(
1963
);
G.
Porter
and
P.
Suppan
,
Trans. Faraday Soc.
61
,
1664
(
1965
);
B. M.
Baughman
,
E.
Stennett
,
R. E.
Lipner
,
A. C.
Rudawsky
, and
S. J.
Schmidtke
,
J. Phys. Chem. A
113
,
8011
(
2009
);
[PubMed]
B. K.
Shah
,
M. A. J.
Rodgers
, and
D. C.
Neckers
,
J. Phys. Chem. A
108
,
6087
(
2004
);
P. J.
Wagner
,
A. E.
Kempainen
, and
H. N.
Schott
,
J. Am. Chem. Soc.
95
,
5604
(
1973
);
N. J.
Turro
,
V.
Ramamurthy
, and
J. C.
Scaiano
,
Modern Molecular Photochemistry of Organic Molecules
(
University Science Books
,
Sausalito
,
2010
).
41.
L. J.
Bellamy
and
R. L.
Williams
,
Trans. Faraday Soc.
55
,
14
(
1959
);
P.
Wagner
and
B. S.
Park
, in
Organic Photochemistry
, edited by
A.
Padwa
(
Marcel Dekker
,
New York
,
1991
), pp.
227
366
.
42.
Y.
Du
,
J.
Xie
,
M.
Li
, and
D. L.
Phillips
,
J. Phys. Chem. A
113
,
3344
(
2009
);
[PubMed]
T.
Tahara
,
H.
Hamaguchi
, and
M.
Tasumi
,
J. Phys. Chem.
91
,
5875
(
1987
).
43.
J. E.
Elenewski
and
J. C.
Hackett
,
J. Chem. Phys.
138
,
224308
(
2013
).
44.
W. L.
Jorgensen
,
D. S.
Maxwell
, and
J.
Tirado-Rives
,
J. Am. Chem. Soc.
118
,
11225
(
1996
);
W. L.
Jorgensen
and
J.
Tirado-Rives
,
Proc. Natl. Acad. Sci. U. S. A.
102
,
6665
(
2005
).
[PubMed]
45.
W. L.
Jorgensen
,
J. Phys. Chem. B
119
,
624
(
2015
), and references therein.
46.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
);
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
);
B.
Miehlich
,
A.
Savin
,
H.
Stoll
, and
H.
Preuss
,
Chem. Phys. Lett.
157
,
200
(
1989
);
S. H.
Vosko
,
L.
Wilk
, and
M.
Nusair
,
Can. J. Phys.
58
,
1200
(
1980
);
T. H.
Dunning
,Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
);
R. A.
Kendall
,
T. H.
Dunning
,Jr.
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
);
J.
Tomasi
,
B.
Mennucci
, and
R.
Cammi
,
Chem. Rev.
105
,
2999
(
2005
).
[PubMed]
47.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
,
G. E.
Scuseria
,
M. A.
Robb
,
J. R.
Cheeseman
,
G.
Scalmani
,
V.
Barone
,
B.
Mennucci
,
G. A.
Petersson
,
H.
Nakatsuji
,
M.
Caricato
,
X.
Li
,
H. P.
Hratchian
,
A. F.
Izmaylov
,
J.
Bloino
,
G.
Zheng
,
J. L.
Sonnenberg
,
M.
Hada
,
M.
Ehara
,
K.
Toyota
,
R.
Fukuda
,
J.
Hasegawa
,
M.
Ishida
,
T.
Nakajima
,
Y.
Honda
,
O.
Kitao
,
H.
Nakai
,
T.
Vreven
,
J. A.
Montgomery
, Jr.
,
J. E.
Peralta
,
F.
Ogliaro
,
M.
Bearpark
,
J. J.
Heyd
,
E.
Brothers
,
K. N.
Kudin
,
V. N.
Staroverov
,
T.
Keith
,
R.
Kobayashi
,
J.
Normand
,
K.
Raghavachari
,
A.
Rendell
,
J. C.
Burant
,
S. S.
Iyengar
,
J.
Tomasi
,
M.
Cossi
,
N.
Rega
,
J. M.
Millam
,
M.
Klene
,
J. E.
Knox
,
J. B.
Cross
,
V.
Bakken
,
C.
Adamo
,
J.
Jaramillo
,
R.
Gomperts
,
R. E.
Stratmann
,
O.
Yazyev
,
A. J.
Austin
,
R.
Cammi
,
C.
Pomelli
,
J. W.
Ochterski
,
R. L.
Martin
,
K.
Morokuma
,
V. G.
Zakrzewski
,
G. A.
Voth
,
P.
Salvador
,
J. J.
Dannenberg
,
S.
Dapprich
,
A. D.
Daniels
,
O.
Farkas
,
J. B.
Foresman
,
J. V.
Ortiz
,
J.
Cioslowski
, and
D. J.
Fox
, gaussian 09, Revision C.01, Gaussian, Inc., Wallingford, CT, 2010.
48.
J. P.
Merrick
,
D.
Moran
, and
L.
Radom
,
J. Phys. Chem. A
111
,
11683
(
2007
).
49.
M. H.
Jamróz
, Vibrational Energy Distribution Analysis VEDA 4, VEDA, Warsaw, 2004–2010 ;
M. H.
Jamróz
,
Spectrochim. Acta, A
114
,
220
(
2013
).
50.
F.
Fursche
and
R.
Ahlrichs
,
J. Chem. Phys.
117
,
7433
(
2002
);
G.
Scalmani
,
M. J.
Frisch
,
B.
Mennucci
,
J.
Tomasi
,
R.
Cammi
, and
V.
Barone
,
J. Chem. Phys.
124
,
094107
(
2006
).
51.
A. E.
Reed
,
L. A.
Curtiss
, and
F.
Weinhold
,
Chem. Rev.
88
,
899
(
1988
).
52.
H. J. C.
Berendsen
,
D. V. D.
Spoel
, and
R. V.
Drunen
,
Comput. Phys. Commun.
91
,
43
(
1995
);
S.
Pronk
,
S.
Pall
,
R.
Schulz
,
P.
Larsson
,
P.
Bjelkmar
,
R.
Apostolov
,
M. R.
Shirts
,
J. C.
Smith
,
P. M.
Kasson
,
D. V. D.
Spoel
,
B.
Hess
, and
E.
Lindahl
,
Bioinformatics
29
,
845
(
2013
);
[PubMed]
D. V. D.
Spoel
,
E.
Lindahl
,
B.
Hess
,
G.
Groenhof
,
A. E.
Mark
, and
H. J. C.
Berendsen
,
J. Comput. Chem.
26
,
1701
(
2005
);
[PubMed]
B.
Hess
,
C.
Kutzner
,
D. V. D.
Spoel
, and
E.
Lindahl
,
J. Chem. Theory Comput.
4
,
435
(
2008
);
[PubMed]
S.
Páll
,
M.
Abraham
,
C.
Kutzner
,
B.
Hess
, and
E.
Lindahl
, “
Tackling exascale software challenges in molecular dynamics simulations with GROMACS
,” in
Solving Software Challenges for Exascale
, edited by
S.
Markidis
and
E.
Laure
,
Lecture Notes in Computer Science
(
Springer International Publishing
,
2015
), Vol.
8759
.
53.
C. M.
Breneman
and
K. B.
Wiberg
,
J. Comput. Chem.
11
,
361
(
1990
).
54.
See supplementary material at http://dx.doi.org/10.1063/1.4941058 for partial charge of Bzp (parameterization for OPLS force field), the van der Waals parameters for Bzp, bond stretching, and angle bending force constants of Bzp (parameterization for OPLS force field), torsional potential energies obtained byab initiocalculations, torsional parameterization of Bzp for OPLS force field, the first solvation shell of Bzp in ACN, MeOH, and EtOH solvents, the computed and experimental structure of Bzp, vibrational assignments of Bzp, Raman spectra of Bzp in different solvents, 2nd order perturbative NBO analysis of Bzp-MeOH complex in the S0state, the C=O stretching frequency of Bzp with implicit and explicit solvent models, empirical solvent polarity for the micro-environment of the dangling carbonyl group of Bzp in protic solvents absorption spectra of Bzp in various solvents, electronic assignments of Bzp in HEX and ACN solvents, Frontier Molecular Orbitals (FMO) of Bzp, correlation plot of >C=O stretching frequency and band I transition, radial distribution functions for Bzp in EtOH solvent, hydrogen bond analysis of Bzp in MeOH and EtOH solvents, histogram plot of hydrogen bonded Bzp clusters in MeOH and EtOH solvents, selected snapshots of Bzp in ACN, MeOH, and EtOH solvent clusters, resonance canonical structure of Bzp in the S0state, the snapshots of molecular dynamics and simulation of Bzp in MeOH solvent, electron density analysis of band I and II electronic transitions, vertical excitation energies of Bzp in protic solvents, natural population analysis of Bzp in S0, S1, and S2 states, and solvatochromic shifts of band I in MeOH solvent.
55.
J.
Wang
,
R. M.
Wolf
,
J. W.
Caldwell
,
P. A.
Kollman
, and
D. A.
Case
,
J. Comput. Chem.
25
,
1157
(
2004
).
56.
H. J. C.
Berendsen
,
J. P. M.
Postma
,
W. F. V.
Gunsteren
,
A.
DiNola
, and
J. R.
Haak
,
J. Chem. Phys.
81
,
3684
(
1984
).
57.
W. C.
Swope
,
H. C.
Anderson
,
P. H.
Berens
, and
K. R.
Wilson
,
J. Chem. Phys.
76
,
637
(
1982
).
58.
W. G.
Hoover
,
A. J. C.
Ladd
, and
B.
Moran
,
Phys. Rev. Lett.
48
,
1818
(
1982
);
S.
Nose
,
J. Chem. Phys.
511
(
1984
);
W. G.
Hoover
,
Phys. Rev. A
1695
(
1985
);
M.
Parinello
and
A.
Rahman
,
J. Appl. Phys.
52
,
7182
(
1981
).
59.
U.
Essman
,
L.
Perera
,
M. L.
Berkowitz
,
T.
Darden
,
H.
Lee
, and
L. G.
Pedersen
,
J. Chem. Phys.
103
,
8577
(
1995
).
60.
B.
Hess
,
H.
Bekker
,
H. J. C.
Berendsen
, and
J. G. E. M.
Fraaije
,
J. Comput. Chem.
18
,
1463
(
1997
).
61.
P.
Bour
and
T. A.
Keiderling
,
J. Chem. Phys.
117
,
4126
(
2002
);
J.
Hudecova
,
K. H.
Hopmann
, and
P.
Bour
,
J. Phys. Chem. B
116
,
336
(
2012
).
[PubMed]
62.
P.
Bour
,
Collect. Czech. Chem. Commun.
70
,
1315
(
2005
).
63.
S.
Yamamoto
,
M.
Straka
,
H.
Watarai
, and
P.
Bour
,
Phys. Chem. Chem. Phys.
12
,
11021
(
2010
).
64.
E. B.
Fleischer
,
N.
Sung
, and
S.
Hawkinson
,
J. Phys. Chem.
72
,
4311
(
1968
).
65.
M.
Kasha
,
Discuss. Faraday Soc.
14
,
1950
;
G. J.
Brealey
and
M.
Kasha
,
J. Am. Chem. Soc.
77
,
4462
(
1955
).
66.
H.
McConnell
,
J. Chem. Phys.
20
,
700
(
1952
).
67.
G. C.
Pimentel
,
J. Am. Chem. Soc.
79
,
3323
(
1957
).
68.
M.
Ito
,
K.
Inuzuka
, and
S.
Imanishi
,
J. Am. Chem. Soc.
82
,
1317
(
1960
).
69.
A. M. J. J.
Bonvin
,
M.
Sunnerhagen
,
G.
Otting
, and
W. F. V.
Gunsteren
,
J. Mol. Biol.
282
,
859
(
1998
);
[PubMed]
S.
Woutersen
,
Y.
Mu
,
G.
Stock
, and
P.
Hamm
,
Chem. Phys.
266
,
137
(
2001
).
70.
K.
Hermansson
,
J. Phys. Chem. A
106
,
4695
(
2002
).
71.
H.
Morrison
,
W. L.
Jorgensen
,
B.
Bigot
,
D.
Severance
,
Y.
Munoz-Sola
,
R.
Strommen
, and
B.
Pandey
,
J. Chem. Educ.
62
,
298
(
1985
).
72.
E.
Buncel
and
S.
Rajagopal
,
Acc. Chem. Res.
23
,
1990
(
1990
).
73.
R.
Letrun
and
E.
Vauthey
,
J. Phys. Chem. Lett.
5
,
1685
(
2014
).

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