The photodissociation of the water dimer in the à band: A twelve-dimensional quasiclassical study
- 14 April 2008
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 128 (14), 144313
- https://doi.org/10.1063/1.2868775
Abstract
The quasiclassical absorptionspectrum of the water dimer in the A ̃ band was calculated taking into account motion in all degrees of freedom of the system. The ab initioexcited state potentials employed were interpolated by the modified Shepard interpolation method using QMRCI energies and state-averaged MCSCF gradients and Hessians. The ground state vibrational wavefunction was variationally calculated using an adiabatic separation between the high and low frequency normal modes of the system. The calculated spectrum of water dimer shows a clear blueshift with respect to the monomer, but also a small red tail, in agreement with the prediction by Harvey et al. [J. Chem. Phys.109, 8747 (1998)]. Previous three-dimensional model studies of the photodissociation of the water dimer by Valenzano et al. [J. Chem. Phys.123, 034303 (2005)] did not show this red tail. A thorough analysis of the dependence of the spectrum on the modes coupled explicitly in the calculation of the spectrum shows that the red tail is due to coupling between the intramolecular stretch vibrations on different monomers.Keywords
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