Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy

Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrödinger equation with a Hamilto...

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Bibliographic Details
Published in:The Journal of chemical physics 2008-05, Vol.128 (19), p.191103-191103-5
Main Authors: Paarmann, A., Hayashi, T., Mukamel, S., Miller, R. J. D.
Format: Article
Language:English
Subjects:
Chemistry, Physical - methods
Communications
Diffusion
Energy Transfer
Hydrogen Bonding
Infrared Rays
Models, Chemical
Models, Statistical
Photons
Spectrophotometry, Infrared - methods
Time Factors
Water - chemistry
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Summary:Two-dimensional infrared photon echo and pump probe studies of the OH stretch vibration provide a sensitive probe of the correlations and couplings in the hydrogen bond network of liquid water. The nonlinear response is simulated using numerical integration of the Schrödinger equation with a Hamiltonian constructed to explicitly treat intermolecular coupling and nonadiabatic effects in the highly disordered singly and doubly excited vibrational exciton manifolds. The simulated two-dimensional spectra are in close agreement with our recent experimental results. The high sensitivity of the OH stretch vibration to the bath dynamics is found to arise from intramolecular mixing between states in the two-dimensional anharmonic OH stretch potential. Surprisingly small intermolecular couplings reproduce the experimentally observed intermolecular energy transfer times.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.2919050