The HOOH UV spectrum: Importance of the transition dipole moment and torsional motion from semiclassical calculations on an ab initio potential energy surface
Journal of Chemical Physics, 132 (8):
084304 (January 2010)DOI: 10.1063/1.3317438
Abstract
The absorption cross section of HOOH, a starting point for larger ROOH, was calculated using the "Wigner method." Calculations use the Wigner transform of ground state wave functions and classical approximations for excited state wave functions. Potential energy and transition dipole moment surfaces were calculated using the equation-of-motion coupled-cluster singles and doubles method over an extended Franck-Condon region. The first two O-O stretches and the first five HOOH torsional levels are included. This study also addresses two fundamental questions about ROOH photodissociation. The long wavelength (A) over tilde (1)A:(B) over tilde B-1 excited state preference has been measured from dynamics experiments, but a Franck-Condon overlap explanation has not been directly verified. A moderate barrier to HOOH torsional motion and excited state dynamics affect the temperature dependence in the UV spectrum. Based on these initial findings for HOOH, photodissociation of large ROOH cannot be eliminated as an important factor for ozone and particulate matter production seen in both ambient and laboratory studies. (C) 2010 American Institute of Physics. doi:10.1063/1.3317438