title: Probing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy.
abstract: 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 Schrodinger 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.
authors.affiliation: Institute for Optical Sciences and Departments of Physics and Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
authors.forename: A
authors.initials: A
authors.lastname: Paarmann
authors.forename: T
authors.initials: T
authors.lastname: Hayashi
authors.forename: S
authors.initials: S
authors.lastname: Mukamel
authors.forename: R J D
authors.initials: RJ
authors.lastname: Miller
mesh_terms: D002627:Chemistry, Physical / Q000379:methods*; D004058:Diffusion; D004735:Energy Transfer; D006860:Hydrogen Bonding; D007259:Infrared Rays; D008956:Models, Chemical; D015233:Models, Statistical; D017785:Photons; D013055:Spectrophotometry, Infrared / Q000379:methods*; D013997:Time Factors; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water