The coupling between the symmetric (νs) and antisymmetric (νa) OD stretch modes of monomeric D2O in CHCl3 is investigated using polarization-dependent two-dimensional infrared (2D IR) spectroscopy supported by numerical 2D IR simulations based on the exciton-band theory. The relationship between the local modes’ and the exciton states’ parameters is systematically studied, including center frequencies, diagonal anharmonicities, coupling, and off-diagonal anharmonicity. The mean coupling between νs and νa is accurately evaluated to be −49.96 ± 0.14 cm−1. The degree of relaxation in the harmonic approximation is quantified, and the angle between the exciton-state dipoles is accurately evaluated to be 101.4° ± 3.6°. In addition, the effect of the local-mode frequency correlation on the resulting exciton-state frequency correlation and the spectral shape of the linear and 2D IR spectra are also investigated.
REFERENCES
1.
G. A.
Jeffrey
and W.
Saenger
, Hydrogen Bonding in Biological Structures
, 1st ed.
(Springer-Verlag
, Berlin
, 1994
).2.
S. K.
Pal
and A. H.
Zewail
, “Dynamics of water in biological recognition
,” Chem. Rev.
104
, 2099
–2123
(2004
).3.
F.
Perakis
, L.
De Marco
, A.
Shalit
, F.
Tang
, Z. R.
Kann
, T. D.
Kühne
, R.
Torre
, M.
Bonn
, and Y.
Nagata
, “Vibrational spectroscopy and dynamics of water
,” Chem. Rev.
116
, 7590
–7607
(2016
).4.
K.
Ramasesha
, S. T.
Roberts
, R. A.
Nicodemus
, A.
Mandal
, and A.
Tokmakoff
, “Ultrafast 2D IR anisotropy of water reveals reorientation during hydrogen-bond switching
,” J. Chem. Phys.
135
, 054509
(2011
).5.
J. C.
Deàk
, L. K.
Iwaki
, S. T.
Rhea
, and D. D.
Dlott
, “Ultrafast infrared-Raman studies of vibrational energy redistribution in polyatomic liquids
,” J. Raman Spectrosc.
31
, 263
–274
(2000
).6.
C. P.
Lawrence
and J. L.
Skinner
, “Vibrational spectroscopy of HOD in liquid D2O. I. Vibrational energy relaxation
,” J. Chem. Phys.
117
, 5827
–5838
(2002
).7.
C. P.
Lawrence
and J. L.
Skinner
, “Vibrational spectroscopy of HOD in liquid D2O. III. Spectral diffusion, and hydrogen-bonding and rotational dynamics
,” J. Chem. Phys.
118
, 264
–272
(2003
).8.
J. J.
Loparo
, S. T.
Roberts
, and A.
Tokmakoff
, “Multidimensional infrared spectroscopy of water. II. Hydrogen bond switching dynamics
,” J. Chem. Phys.
125
, 194522
(2006
).9.
J. J.
Loparo
, S. T.
Roberts
, and A.
Tokmakoff
, “Multidimensional infrared spectroscopy of water. I. Vibrational dynamics in two-dimensional IR line shapes
,” J. Chem. Phys.
125
, 194521
(2006
).10.
S.
Woutersen
, U.
Emmerichs
, and H. J.
Bakker
, “Femtosecond mid-IR pump-probe spectroscopy of liquid water: Evidence for a two-component structure
,” Science
278
, 658
–660
(1997
).11.
R.
Jimenez
, G. R.
Fleming
, P. V.
Kumar
, and M.
Maroncelli
, “Femtosecond solvation dynamics of water
,” Nature
369
, 471
–473
(1994
).12.
P.
Hamm
, M.
Lim
, and R. M.
Hochstrasser
, “Structure of the amide I band of peptides measured by femtosecond nonlinear-infrared spectroscopy
,” J. Phys. Chem. B
102
, 6123
–6138
(1998
).13.
M.
Khalil
, N.
Demirdöven
, and A.
Tokmakoff
, “Coherent 2D IR spectroscopy: Molecular structure and dynamics in solution
,” J. Phys. Chem. A
107
, 5258
–5279
(2003
).14.
Y. S.
Kim
and R. M.
Hochstrasser
, “Applications of 2D IR spectroscopy to peptides, proteins, and hydrogen-bond dynamics
,” J. Phys. Chem. B
113
, 8231
–8251
(2009
).15.
P.
Hamm
and M.
Zanni
, Concepts and Methods of 2D Infrared Spectroscopy
(Cambridge University Press
, New York
, 2011
).16.
L.
De Marco
, W.
Carpenter
, H.
Liu
, R.
Biswas
, J. M.
Bowman
, and A.
Tokmakoff
, “Differences in the vibrational dynamics of H2O and D2O: Observation of symmetric and antisymmetric stretching vibrations in heavy water
,” J. Phys. Chem. Lett.
7
, 1769
–1774
(2016
).17.
M.
Cho
, “Coherent two-dimensional optical spectroscopy
,” Chem. Rev.
108
, 1331
–1418
(2008
).18.
J.
Zheng
, K.
Kwak
, and M. D.
Fayer
, “Ultrafast two-dimensional IR vibrational echo spectroscopy
,” Acc. Chem. Res.
40
, 75
–83
(2007
).19.
M. C.
Asplund
, M. T.
Zanni
, and R. M.
Hochstrasser
, “Two-dimensional infrared spectroscopy of peptides by phase-controlled femtosecond vibrational photon echoes
,” Proc. Natl. Acad. Sci. U. S. A.
97
, 8219
–8224
(2000
).20.
T. l. C.
Jansen
, D.
Cringus
, and M. S.
Pshenichnikov
, “Dissimilar dynamics of coupled water vibrations
,” J. Phys. Chem. A
113
, 6260
–6265
(2009
).21.
O.
Golonzka
, M.
Khalil
, N.
Demirdöven
, and A.
Tokmakoff
, “Coupling and orientation between anharmonic vibrations characterized with two-dimensional infrared vibrational echo spectroscopy
,” J. Chem. Phys.
115
, 10814
–10828
(2001
).22.
M.
Khalil
, N.
Demirdöven
, and A.
Tokmakoff
, “Obtaining absorptive line shapes in two-dimensional infrared vibrational correlation spectra
,” Phys. Rev. Lett.
90
, 047401
(2003
).23.
M.
Khalil
, N.
Demirdöven
, and A.
Tokmakoff
, “Vibrational coherence transfer characterized with Fourier-transform 2D IR spectroscopy
,” J. Chem. Phys.
121
, 362
–373
(2004
).24.
F.
Yang
, X.
Dong
, M.
Feng
, J.
Zhao
, and J.
Wang
, “Central-metal effect on intramolecular vibrational energy transfer of M(CO)5Br (M = Mn, Re) probed by two-dimensional infrared spectroscopy
,” Phys. Chem. Chem. Phys.
20
, 3637
–3647
(2018
).25.
K.
Kwak
, S.
Park
, I. J.
Finkelstein
, and M. D.
Fayer
, “Frequency-frequency correlation functions and apodization in two-dimensional infrared vibrational echo spectroscopy: A new approach
,” J. Chem. Phys.
127
, 124503
(2007
).26.
D. B.
Wong
, C. H.
Giammanco
, E. E.
Fenn
, and M. D.
Fayer
, “Dynamics of isolated water molecules in a sea of ions in a room temperature ionic liquid
,” J. Phys. Chem. B
117
, 623
–635
(2013
).27.
Y. S.
Kim
and R. M.
Hochstrasser
, “Chemical exchange 2D IR of hydrogen-bond making and breaking
,” Proc. Natl. Acad. Sci. U. S. A.
102
, 11185
–11190
(2005
).28.
S.
Woutersen
, Y.
Mu
, G.
Stock
, and P.
Hamm
, “Hydrogen-bond lifetime measured by time-resolved 2D-IR spectroscopy: N-methylacetamide in methanol
,” Chem. Phys.
266
, 137
–147
(2001
).29.
J.
Zheng
, K.
Kwak
, J.
Asbury
, X.
Chen
, I. R.
Piletic
, and M. D.
Fayer
, “Ultrafast dynamics of solute-solvent complexation observed at thermal equilibrium in real time
,” Science
309
, 1338
–1343
(2005
).30.
H.
Graener
and G.
Seifert
, “Vibrational and orientational relaxation of monomeric water molecules in liquids
,” J. Chem. Phys.
98
, 36
–45
(1993
).31.
A. S.
Davydov
, Theory of Molecular Excitons
(Plenum Press
, New York
, 1971
).32.
R. M.
Hochstrasser
, “Two-dimensional IR-spectroscopy: Polarization anisotropy effects
,” Chem. Phys.
266
, 273
–284
(2001
).33.
G. Y.
Jin
and Y. S.
Kim
, “Phase-resolved heterodyne-detected transient grating enhances the capabilities of 2D IR echo spectroscopy
,” J. Phys. Chem. A
121
, 1007
–1011
(2017
).34.
Y. S.
Kim
, J.
Wang
, and R. M.
Hochstrasser
, “Two-dimensional infrared spectroscopy of the alanine dipeptide in aqueous solution
,” J. Phys. Chem. B
109
, 7511
–7521
(2005
).35.
J. G.
Seol
, H.
Kwon
, G. Y.
Jin
, J.
Moon
, C.
Yi
, and Y. S.
Kim
, “Scattering elimination of heterodyne-detected two-dimensional infrared spectra using choppers and shutters
,” J. Phys. Chem. A
123
, 10837
–10843
(2019
).36.
N.-H.
Ge
, M. T.
Zanni
, and R. M.
Hochstrasser
, “Effects of vibrational frequency correlations on two-dimensional infrared spectra
,” J. Phys. Chem. A
106
, 962
–972
(2002
).37.
T.
Köddermann
, C.
Wertz
, A.
Heintz
, and R.
Ludwig
, “The association of water in ionic liquids: A reliable measure of polarity
,” Angew. Chem., Int. Ed.
45
, 3697
–3702
(2006
).38.
D.-x.
Zhou
, Q.-s.
Wei
, H.-t.
Bian
, and J.-r.
Zheng
, “Direct vibrational energy transfer in monomeric water probed with ultrafast two dimensional infrared spectroscopy
,” Chin. J. Chem. Phys.
30
, 619
–625
(2017
).39.
M. T.
Zanni
, N.-H.
Ge
, Y. S.
Kim
, and R. M.
Hochstrasser
, “Two-dimensional IR spectroscopy can be designed to eliminate the diagonal peaks and expose only the crosspeaks needed for structure determination
,” Proc. Natl. Acad. Sci. U. S. A.
98
, 11265
–11270
(2001
).40.
C. S.
Peng
, K. C.
Jones
, and A.
Tokmakoff
, “Anharmonic vibrational modes of nucleic acid bases revealed by 2D IR spectroscopy
,” J. Am. Chem. Soc.
133
, 15650
–15660
(2011
).41.
D. T.
Colbert
and W. H.
Miller
, “A novel discrete variable representation for quantum mechanical reactive scattering via the S‐matrix Kohn method
,” J. Chem. Phys.
96
, 1982
–1991
(1992
).42.
E. J.
Berquist
, C. A.
Daly
, Jr., T.
Brinzer
, K. K.
Bullard
, Z. M.
Campbell
, S. A.
Corcelli
, S.
Garrett-Roe
, and D. S.
Lambrecht
, “Modeling carbon dioxide vibrational frequencies in ionic liquids: I. Ab initio calculations
,” J. Phys. Chem. B
121
, 208
–220
(2017
).43.
D.
Cringus
, T. l. C.
Jansen
, M. S.
Pshenichnikov
, and D. A.
Wiersma
, “Ultrafast anisotropy dynamics of water molecules dissolved in acetonitrile
,” J. Chem. Phys.
127
, 084507
(2007
).© 2023 Author(s). Published under an exclusive license by AIP Publishing.
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