We employ the ab initio molecular dynamics within the surface hopping method to explore the excited-state intramolecular proton transfer taking place on the coupled “bright” S1 (ππ*) and “dark” S2 (nπ*) states of 3-hydroxychromone. The nonadiabatic population transfer between these states via an accessible conical intersection would open up multiple proton transfer pathways. Our findings reveal the keto tautomer formation via S1 on a timescale similar to the O–H in-plane vibrational period (<100 fs). Structural analysis indicates that a few parameters of the five-membered proton transfer geometry that constitute the donor (hydroxyl) and acceptor (carbonyl) groups would be adequate to drive the enol to keto transformation. We also investigate the role of O–H in-plane and out-of-plane vibrational motions in the excited-state dynamics of 3-hydroxychromone.

1.
A.
Weller
,
Z. Elektrochem.
60
,
1144
(
1956
).
2.
J. E.
Kwon
and
S. Y.
Park
,
Adv. Mater.
23
,
3615
(
2011
).
3.
J.
Zhao
,
S.
Ji
,
Y.
Chen
,
H.
Guo
, and
P.
Yang
,
Phys. Chem. Chem. Phys.
14
,
8803
(
2012
).
4.
N.
Suzuki
,
A.
Fukazawa
,
K.
Nagura
,
S.
Saito
,
H.
Kitoh-Nishioka
,
D.
Yokogawa
,
S.
Irle
, and
S.
Yamaguchi
,
Angew. Chem., Int. Ed.
53
,
8231
(
2014
).
5.
V. S.
Padalkar
and
S.
Seki
,
Chem. Soc. Rev.
45
,
169
(
2016
).
6.
A. C.
Sedgwick
,
L.
Wu
,
H.-H.
Han
,
S. D.
Bull
,
X.-P.
He
,
T. D.
James
,
J. L.
Sessler
,
B. Z.
Tang
,
H.
Tian
, and
J.
Yoon
,
Chem. Soc. Rev.
47
,
8842
(
2018
).
7.
S. Y.
Arzhantsev
,
S.
Takeuchi
, and
T.
Tahara
,
Chem. Phys. Lett.
330
,
83
(
2000
).
8.
P.-T.
Chou
,
Y.-C.
Chen
,
W.-S.
Yu
,
Y.-H.
Chou
,
C.-Y.
Wei
, and
Y.-M.
Cheng
,
J. Phys. Chem. A
105
,
1731
(
2001
).
9.
S.
Lochbrunner
,
T.
Schultz
,
M.
Schmitt
,
J. P.
Shaffer
,
M. Z.
Zgierski
, and
A.
Stolow
,
J. Chem. Phys.
114
,
2519
(
2001
).
10.
V. V.
Shynkar
,
Y.
Mély
,
G.
Duportail
,
E.
Piémont
,
A. S.
Klymchenko
, and
A. P.
Demchenko
,
J. Phys. Chem. A
107
,
9522
(
2003
).
11.
C. H.
Kim
and
T.
Joo
,
Phys. Chem. Chem. Phys.
11
,
10266
(
2009
).
12.
T.
Iijima
,
A.
Momotake
,
Y.
Shinohara
,
T.
Sato
,
Y.
Nishimura
, and
T.
Arai
,
J. Phys. Chem. A
114
,
1603
(
2010
).
13.
A.
Corani
,
A.
Pezzella
,
T.
Pascher
,
T.
Gustavsson
,
D.
Markovitsi
,
A.
Huijser
,
M.
d’Ischia
, and
V.
Sundström
,
J. Phys. Chem. Lett.
4
,
1383
(
2013
).
14.
V. I.
Tomin
,
A. P.
Demchenko
, and
P.-T.
Chou
,
J. Photochem. Photobiol., C
22
,
1
(
2015
).
15.
P. K.
Sengupta
and
M.
Kasha
,
Chem. Phys. Lett.
68
,
382
(
1979
).
16.
B.
An
,
S.
Feng
,
K.
Wen
,
W.
Wu
,
H.
Yuan
,
Q.
Zhu
,
X.
Guo
, and
J.
Zhang
,
Org. Electron.
45
,
1
(
2017
).
17.
Q.
Wei
,
Q.
Zhou
,
M.
Zhao
,
M.
Zhang
, and
P.
Song
,
J. Lumin.
183
,
7
(
2017
).
18.
Y.
Liu
,
J.
Zhao
,
Y.
Wang
,
J.
Tian
,
X.
Fei
, and
H.
Wang
,
J. Mol. Liq.
233
,
303
(
2017
).
19.
Y.
Qi
,
M.
Lu
,
Y.
Wang
,
Z.
Tang
,
Z.
Gao
,
J.
Tian
,
X.
Fei
,
Y.
Li
, and
J.
Liu
,
Org. Chem. Front.
6
,
3136
(
2019
).
20.
D.
Yang
,
W.
Liu
,
L.
Kong
,
Q.
Zhang
, and
Y.
Liu
,
Chem. Phys. Lett.
744
,
137226
(
2020
).
21.
L.
Wang
,
Y.
Wang
,
Q.
Zhang
, and
J.
Zhao
,
J. Phys. Org. Chem.
33
,
e4020
(
2020
).
22.
C.
Li
,
Y.
Yang
,
C.
Ma
, and
Y.
Liu
,
RSC Adv.
6
,
5134
(
2016
).
23.
Y.
Peng
,
Y.
Ye
,
X.
Xiu
, and
S.
Sun
,
J. Phys. Chem. A
121
,
5625
(
2017
).
24.
Y.
Ma
,
Y.
Yang
,
R.
Lan
, and
Y.
Li
,
J. Phys. Chem. C
121
,
14779
(
2017
).
25.
J.
Hao
and
Y.
Yang
,
J. Phys. Org. Chem.
32
,
e3903
(
2019
).
26.
W.
Domcke
,
D. R.
Yarkony
, and
H.
Köppel
,
Conical Intersections
(
World Scientific
,
2011
).
27.
S.
Matsika
, “
Conical intersections in molecular systems
,” in
Reviews in Computational Chemistry
(
John Wiley & Sons, Ltd.
,
2007
), Chap. 2, pp.
83
124
.
28.
A.
Perveaux
,
M.
Lorphelin
,
B.
Lasorne
, and
D.
Lauvergnat
,
Phys. Chem. Chem. Phys.
19
,
6579
(
2017
).
29.
N.
Anand
,
S. V. K.
Isukapalli
, and
S. R.
Vennapusa
,
J. Comput. Chem.
41
,
1068
(
2020
).
30.
H.-D.
Meyer
,
U.
Manthe
, and
L. S.
Cederbaum
,
Chem. Phys. Lett.
165
,
73
(
1990
).
31.
U.
Manthe
,
H.-D.
Meyer
, and
L. S.
Cederbaum
,
J. Chem. Phys.
97
,
3199
(
1992
).
32.
M. H.
Beck
,
A.
Jäckle
,
G. A.
Worth
, and
H.-D.
Meyer
,
Phys. Rep.
324
,
1
(
2000
).
33.
34.
H.
Wang
and
H.-D.
Meyer
,
J. Chem. Phys.
149
,
044119
(
2018
).
35.
M.
Itoh
,
Pure Appl. Chem.
65
,
1629
(
1993
).
36.
G. A.
Brucker
and
D. F.
Kelley
,
J. Phys. Chem.
91
,
2862
2866
(
1987
).
37.
K.
Chevalier
,
A.
Grün
,
A.
Stamm
,
Y.
Schmitt
,
M.
Gerhards
, and
R.
Diller
,
J. Phys. Chem. A
117
,
11233
(
2013
).
38.
I.
Antol
,
M.
Vazdar
,
M.
Barbatti
, and
M.
Eckert-Maksić
,
Chem. Phys.
349
,
308
(
2008
), part of the Special Issue: Electron Correlation and Molecular Dynamics for Excited States and Photochemistry.
39.
J. D.
Coe
and
T. J.
Martínez
,
J. Phys. Chem. A
110
,
618
(
2006
).
40.
R.
Crespo-Otero
and
M.
Barbatti
,
J. Chem. Phys.
134
,
164305
(
2011
).
41.
M. E.
Corrales
,
V.
Loriot
,
G.
Balerdi
,
J.
González-Vázquez
,
R.
de Nalda
,
L.
Bañares
, and
A. H.
Zewail
,
Phys. Chem. Chem. Phys.
16
,
8812
(
2014
).
42.
Y.
Lei
,
H.
Wu
,
X.
Zheng
,
G.
Zhai
, and
C.
Zhu
,
J. Photochem. Photobiol., A
317
,
39
(
2016
).
43.
M. L.
Murillo-Sánchez
,
S.
Marggi Poullain
,
J.
González-Vázquez
,
M. E.
Corrales
,
G.
Balerdi
, and
L.
Bañares
,
Chem. Phys. Lett.
683
,
22
(
2017
), part of the Special Issue: Ahmed Zewail (1946–2016) Commemoration Issue of Chemical Physics Letters.
44.
J.
Jankowska
,
M.
Barbatti
,
J.
Sadlej
, and
A. L.
Sobolewski
,
Phys. Chem. Chem. Phys.
19
,
5318
(
2017
).
45.
R.
Salaeh
,
C.
Prommin
,
W.
Chansen
,
K.
Kerdpol
,
R.
Daengngern
, and
N.
Kungwan
,
J. Mol. Liq.
252
,
428
(
2018
).
46.
C.
Sukpattanacharoen
,
R.
Salaeh
,
V.
Promarak
,
D.
Escudero
, and
N.
Kungwan
,
J. Mol. Struct.
1195
,
280
(
2019
).
47.
J. D.
Coe
,
B. G.
Levine
, and
T. J.
Martínez
,
J. Phys. Chem. A
111
,
11302
(
2007
).
48.
A. J. A.
Aquino
,
F.
Plasser
,
M.
Barbatti
, and
H.
Lischka
,
Croat. Chem. Acta
82
,
105
(
2009
).
49.
N.
Kungwan
,
F.
Plasser
,
A. J. A.
Aquino
,
M.
Barbatti
,
P.
Wolschann
, and
H.
Lischka
,
Phys. Chem. Chem. Phys.
14
,
9016
(
2012
).
50.
L.
Du
and
Z.
Lan
,
J. Chem. Theory Comput.
11
,
1360
(
2015
).
51.
Y.
Ootani
,
A.
Satoh
,
Y.
Harabuchi
, and
T.
Taketsugu
,
J. Comput. Chem.
41
,
1549
(
2020
).
52.
C.-X.
Li
,
W.-W.
Guo
,
B.-B.
Xie
, and
G.
Cui
,
J. Chem. Phys.
145
,
074308
(
2016
).
53.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
54.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
55.
C.
Hättig
and
F.
Weigend
,
J. Chem. Phys.
113
,
5154
(
2000
).
56.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
,
G. E.
Scuseria
,
M. A.
Robb
,
J. R.
Cheeseman
,
G.
Scalmani
,
V.
Barone
,
G. A.
Petersson
,
H.
Nakatsuji
,
X.
Li
,
M.
Caricato
,
A. V.
Marenich
,
J.
Bloino
,
B. G.
Janesko
,
R.
Gomperts
,
B.
Mennucci
,
H. P.
Hratchian
,
J. V.
Ortiz
,
A. F.
Izmaylov
,
J. L.
Sonnenberg
,
D.
Williams-Young
,
F.
Ding
,
F.
Lipparini
,
F.
Egidi
,
J.
Goings
,
B.
Peng
,
A.
Petrone
,
T.
Henderson
,
D.
Ranasinghe
,
V. G.
Zakrzewski
,
J.
Gao
,
N.
Rega
,
G.
Zheng
,
W.
Liang
,
M.
Hada
,
M.
Ehara
,
K.
Toyota
,
R.
Fukuda
,
J.
Hasegawa
,
M.
Ishida
,
T.
Nakajima
,
Y.
Honda
,
O.
Kitao
,
H.
Nakai
,
T.
Vreven
,
K.
Throssell
,
J. A.
Montgomery
, Jr.
,
J. E.
Peralta
,
F.
Ogliaro
,
M. J.
Bearpark
,
J. J.
Heyd
,
E. N.
Brothers
,
K. N.
Kudin
,
V. N.
Staroverov
,
T. A.
Keith
,
R.
Kobayashi
,
J.
Normand
,
K.
Raghavachari
,
A. P.
Rendell
,
J. C.
Burant
,
S. S.
Iyengar
,
J.
Tomasi
,
M.
Cossi
,
J. M.
Millam
,
M.
Klene
,
C.
Adamo
,
R.
Cammi
,
J. W.
Ochterski
,
R. L.
Martin
,
K.
Morokuma
,
O.
Farkas
,
J. B.
Foresman
, and
D. J.
Fox
, Gaussian 16, Revision C.01,
Gaussian, Inc.
,
Wallingford, CT
,
2016
.
57.
TURBOMOLE V7.4 2019, a development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989–2007, TURBOMOLE GmbH, since 2007; available from http://www.turbomole.com.
58.
M.
Richter
,
P.
Marquetand
,
J.
González-Vázquez
,
I.
Sola
, and
L.
González
,
J. Chem. Theory Comput.
7
,
1253
(
2011
).
59.
S.
Mai
,
P.
Marquetand
, and
L.
González
,
Wiley Interdiscip. Rev.: Comput. Mol. Sci.
8
,
e1400
(
2018
).
60.
J. P.
Dahl
and
M.
Springborg
,
J. Chem. Phys.
88
,
4535
(
1988
).
61.
R.
Schinke
,
Photodissociation Dynamics: Spectroscopy and Fragmentation of Small Polyatomic Molecules
, Cambridge Monographs on Atomic, Molecular and Chemical Physics (
Cambridge University Press
,
1993
).
62.
M.
Barbatti
and
K.
Sen
,
Int. J. Quantum Chem.
116
,
762
(
2016
).
64.
65.
G.
Granucci
,
M.
Persico
, and
A.
Toniolo
,
J. Chem. Phys.
114
,
10608
(
2001
).
66.
G.
Granucci
and
M.
Persico
,
J. Chem. Phys.
126
,
134114
(
2007
).
67.
G.
Granucci
,
M.
Persico
, and
A.
Zoccante
,
J. Chem. Phys.
133
,
134111
(
2010
).
68.
F.
Neese
,
Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
,
73
(
2012
).
69.
B. G.
Levine
,
J. D.
Coe
, and
T. J.
Martínez
,
J. Phys. Chem. B
112
,
405
(
2008
).
70.
S.
Ash
,
S. P.
De
,
H.
Beg
, and
A.
Misra
,
Mol. Simul.
37
,
914
(
2011
).
71.
A. N.
Bader
,
V. G.
Pivovarenko
,
A. P.
Demchenko
,
F.
Ariese
, and
C.
Gooijer
,
J. Phys. Chem. B
108
,
10589
(
2004
).
72.
J. D.
Hybl
,
A. W.
Albrecht
,
S. M.
Gallagher Faeder
, and
D. M.
Jonas
,
Chem. Phys. Lett.
297
,
307
(
1998
).
73.
F. D.
Fuller
and
J. P.
Ogilvie
,
Annu. Rev. Phys.
66
,
667
(
2015
).

Supplementary Material

You do not currently have access to this content.