Vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation are computed in order to interpret and predict vibronic transitions that are probed in the Vibrationally Promoted Electronic Resonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem., Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformation of time-domain wavepacket autocorrelation functions, respectively. The time-independent approach uses a generalized version of the FCclasses method [F. Santoro et al., J. Chem. Phys. 126, 084509 (2007)]. In the time-dependent approach, autocorrelation functions are obtained by wavepacket propagation and by the evaluation of analytic expressions, within the harmonic approximation including Duschinsky rotation effects. For several medium-sized polyatomic systems, it is shown that selective pre-excitation of particular vibrational modes leads to a redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. This effect is typically most pronounced upon excitation of modes that are significantly displaced during the electronic transition, such as ring distortion modes within an aromatic π-system. Theoretical predictions as to which modes show the strongest VIPER effect are found to be in excellent agreement with experiment.

1.
L. J. G. W.
van Wilderen
and
J.
Bredenbeck
,
Angew. Chem., Int. Ed.
54
,
11624
(
2015
).
2.
J. N.
Mastron
and
A.
Tokmakoff
,
J. Phys. Chem. A
120
,
9178
(
2016
).
3.
T. L.
Courtney
,
Z. W.
Fox
,
K. M.
Slenkamp
, and
M.
Khalil
,
J. Chem. Phys.
143
,
154201
(
2015
).
4.
T. L.
Courtney
,
Z. W.
Fox
,
L.
Estergreen
, and
M.
Khalil
,
J. Phys. Chem. Lett.
6
,
1286
(
2015
).
5.
L. J. G. W.
van Wilderen
,
A. T.
Messmer
, and
J.
Bredenbeck
,
Angew. Chem., Int. Ed.
53
,
2667
(
2014
).
6.
D.
Kern-Michler
,
C.
Neumann
,
N.
Mielke
,
L. J. G. W.
van Wilderen
,
M.
Reinfelds
,
J.
von Cosel
,
A.
Heckel
,
I.
Burghardt
, and
J.
Bredenbeck
, “
Controlling photochemistry via isotopomers and vibrational pre-excitation
” (unpublished).
7.
P.
Klán
,
T.
Šolomek
,
C. G.
Bochet
,
A.
Blanc
,
R.
Givens
,
M.
Rubina
,
V.
Popik
,
A.
Kostikov
, and
J.
Wirz
,
Chem. Rev.
113
,
119
(
2012
).
8.
C.
Park
and
R.
Givens
,
J. Am. Chem. Soc.
119
,
2453
(
1997
).
9.
L. J. G. W.
van Wilderen
,
C.
Neumann
,
A.
Rodrigues-Correia
,
D.
Kern-Michler
,
N.
Mielke
,
M.
Reinfelds
,
A.
Heckel
, and
J.
Bredenbeck
,
Phys. Chem. Chem. Phys.
19
,
6487
(
2017
).
10.
F.
Santoro
,
R.
Improta
,
A.
Lami
,
J.
Bloino
, and
V.
Barone
,
J. Chem. Phys.
126
,
084509
(
2007
).
11.
F.
Santoro
,
A.
Lami
,
R.
Improta
, and
V.
Barone
,
J. Chem. Phys.
126
,
184102
(
2007
).
12.
F.
Santoro
,
A.
Lami
,
R.
Improta
,
J.
Bloino
, and
V.
Barone
,
J. Chem. Phys.
128
,
224311
(
2008
).
13.
H.
Wang
and
M.
Thoss
,
J. Chem. Phys.
119
,
1289
(
2003
).
14.
O.
Vendrell
and
H.-D.
Meyer
,
J. Chem. Phys.
134
,
044135
(
2011
).
15.
H.-D.
Meyer
,
U.
Manthe
, and
L. S.
Cederbaum
,
Chem. Phys. Lett.
165
,
73
(
1990
).
16.
M. H.
Beck
,
A.
Jäckle
,
G. A.
Worth
, and
H.-D.
Meyer
,
Phys. Rep.
324
,
1
(
2000
).
17.
G. A.
Worth
,
H.-D.
Meyer
,
H.
Köppel
,
L. S.
Cederbaum
, and
I.
Burghardt
,
Int. Rev. Phys. Chem.
27
,
569
(
2008
).
18.
F.
Duschinsky
,
Acta Physicochim. U. R. S. S.
7
,
551
(
1937
).
19.
J. R.
Reimers
,
J. Chem. Phys.
115
,
9103
(
2001
).
20.
R.
Borrelli
and
A.
Peluso
,
J. Chem. Phys.
125
,
194308
(
2006
).
21.
J.
Cerezo
,
J.
Zúñiga
,
A.
Requena
,
F. J.
Ávila Ferrer
, and
F.
Santoro
,
J. Chem. Theory Comput.
9
,
4947
(
2013
).
22.
A.
Baiardi
,
J.
Bloino
, and
V.
Barone
,
J. Chem. Phys.
144
,
084114
(
2016
).
23.
J.
Cerezo
and
F.
Santoro
,
J. Chem. Theory Comput.
12
,
4970
(
2016
).
24.
D. J.
Tannor
,
Introduction to Quantum Mechanics: A Time-Dependent Perspective
, 1st ed. (
University Science Books
,
USA
,
2007
).
25.
F.
Santoro
, FCclasses, A Fortran 77 code, available at http://village.pi.iccom.cnr.it/Software.
26.
F.
Santoro
and
A.
Lami
, in
Computational Strategies for Spectroscopy: From Small Molecules to Nano Systems
, edited by
V.
Barone
(
John Wiley & Sons, Inc.
,
2012
), Chap. 10, pp.
475
516
.
27.
F. J.
Avila Ferrer
,
J.
Cerezo
,
J.
Soto
,
R.
Improta
, and
F.
Santoro
,
Comput. Theor. Chem.
1040–1041
,
328
(
2014
).
28.
A.
Baiardi
,
J.
Bloino
, and
V.
Barone
,
J. Chem. Theory Comput.
9
,
4097
(
2013
).
29.
E.
Ianconescu
and
E.
Pollak
,
J. Phys. Chem. A
108
,
7778
(
2004
).
30.
J.
Tatchen
and
E.
Pollak
,
J. Chem. Phys.
128
,
164303
(
2008
).
31.
J.
Tang
,
M. T.
Lee
, and
S. H.
Lin
,
J. Chem. Phys.
119
,
7188
(
2003
).
32.
Y.
Yan
and
S.
Mukamel
,
J. Chem. Phys.
85
,
5908
(
1986
).
33.
S.
Mukamel
,
S.
Abe
, and
R.
Islampour
,
J. Phys. Chem.
89
,
201
(
1985
).
34.
R.
Kubo
and
Y.
Toyozawa
,
Prog. Theor. Phys.
13
,
160
(
1955
).
35.
J.
Huh
and
R.
Berger
,
J. Phys.: Conf. Ser.
380
,
012019
(
2012
).
36.
A.
Baiardi
,
J.
Bloino
, and
V.
Barone
,
J. Chem. Phys.
141
,
114108
(
2014
).
37.
Q.
Peng
,
Y.
Niu
,
C.
Deng
, and
Z.
Shuai
,
Chem. Phys.
370
,
215
(
2010
).
38.
R.
Borrelli
,
A.
Capobianco
, and
A.
Peluso
,
J. Phys. Chem. A
116
,
9934
(
2012
).
39.
M.
Biczysko
,
J.
Bloino
,
F.
Santoro
, and
V.
Barone
, in
Computational Strategies for Spectroscopy: From Small Molecules to Nano Systems
, edited by
V.
Barone
(
John Wiley & Sons, Inc.
,
2012
), Chap. 8, pp.
361
443
.
40.
S.
Mukamel
,
Principles of Nonlinear Optical Spectroscopy
, 1st ed. (
Oxford University Press
,
Oxford
,
1999
).
41.
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
,
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
,
Ö.
Farkas
,
J. B.
Foresman
,
J. V.
Ortiz
,
J.
Cioslowski
, and
D. J.
Fox
, gaussian 09 Revision D.01,
Gaussian, Inc.
,
Wallingford, CT
,
2013
.
42.
J.-D.
Chai
and
M.
Head-Gordon
,
Phys. Chem. Chem. Phys.
10
,
6615
(
2008
).
43.
T.
Yanai
,
D. P.
Tew
, and
N. C.
Handy
,
Chem. Phys. Lett.
393
,
51
(
2004
).
44.
C.
Adamo
and
V.
Barone
,
J. Chem. Phys.
110
,
6158
(
1999
).
45.
F.
Weigend
and
R.
Ahlrichs
,
Phys. Chem. Chem. Phys.
7
,
3297
(
2005
).
46.
F. J. A.
Ferrer
and
F.
Santoro
,
Phys. Chem. Chem. Phys.
14
,
13549
(
2012
).
47.
G. A.
Worth
,
M. H.
Beck
,
A.
Jäckle
,
O.
Vendrell
, and
H.-D.
Meyer
, The MCTDH package, version 8.5.4, see http://mctdh.uni-hd.de/.
48.
W. H.
Press
,
S. A.
Teukolsky
,
W. T.
Vetterling
, and
B. P.
Flannery
,
Numerical Recipes 3rd Edition: The Art of Scientific Computing
, 3rd ed. (
Cambridge University Press
,
New York, NY, USA
,
2007
).
49.
J.
Huh
and
R.
Berger
,
Faraday Discuss.
150
,
363
(
2011
).
50.
H.
Köppel
,
W.
Domcke
, and
L. S.
Cederbaum
, in
Conical Intersections
, edited by
W.
Domcke
,
D. R.
Yarkony
, and
H.
Köppel
(
World Scientific Co.
,
2004
), pp.
323
368
.

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