2-Photon Dissociation of Vibrationally Excited Hd+ - the Inhomogeneous Differential-Equation Approach
Journal
Journal of Chemical Physics
Journal Volume
85
Journal Issue
3
Pages
1403-1411
Date Issued
1986
Author(s)
Abstract
We extend the inhomogenous-differential-equation (IDE) approach of Dalgarno and Lewis for a detailed study of two-photon dissociation (TPD) of HD + from high vibrational levels of the 1sσg electronic state. Contrary to the H2+ case, where the TPD cross sections σL(2) are largest near TPD thresholds and decrease monotonically with increasing photon energy, the HD+ cross sections are characterized by rich resonant and interference structures. We present σL(2) results for TPD from the initial υi=6, 8, 10, 12, 14, 16, and ji=0 levels as weE as from υi=14, ji=0, 2, 4 levels for a wide range of wavelengths of linearly polarized radiation accessible by CO2 and CO lasers. It is found that while there are four TPD pathways, the channel 1sσg(υiji) →ω1sσg (υ,j=ji±1) →ω2pσu(k,jf=j±1) dominates the two-photon process in most of the cases we have studied. Further, the results show that σL(2) increases rather rapidly as the initial vibrational quantum number υi increases, indicating that the hereronuclear diatomic molecules in high vibrational levels can be efficiently two-photon dissociated by IR lasers. Consequently molecular structures near the dissociation limit may be conveniently probed by two-photon spectroscopy-as has indeed been demonstrated recently by experiments. Our σL(2) results thus provide complementary information to the HD+ spectroscopic data obtained recently by Carrington et al. © 1986 American Institute of Physics.
SDGs
Type
journal article