Open AccessProbing intermolecular couplings in liquid water with two-dimensional infrared photon echo spectroscopy
Author(s) -
Alexander Paarmann,
Tomoyuki Hayashi,
Shaul Mukamel,
R. J. Dwayne Miller
Publication year - 2008
Publication title -
the journal of chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.071
H-Index - 357
eISSN - 1089-7690
pISSN - 0021-9606
DOI - 10.1063/1.2919050
Subject(s) - intermolecular force , anharmonicity , intramolecular force , excited state , chemistry , hamiltonian (control theory) , rotational–vibrational coupling , molecular physics , spectroscopy , photon , infrared spectroscopy , infrared , exciton , atomic physics , physics , molecule , quantum mechanics , mathematical optimization , mathematics , organic chemistry , stereochemistry
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.
Accelerating Research
Robert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom
Address
John Eccles HouseRobert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom