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Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(/sup 1/S) + H/sub 2/(B /sup 1/. sigma. /sub u//sup +/)

Thesis/Dissertation ·
OSTI ID:7149023

To further understanding of gas-phase collision dynamics involving electronically-excited molecules, a fully quantum-mechanical study of He + H/sub 2/ (B/sup 1/ ..sigma../sub u//sup +/) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H/sub 2/ (B /sup 1/..sigma../sub u//sup +/). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H/sub 2/ (E,F, /sup 1/..sigma../sub g//sup +/) and with He + H/sub 2/ (X /sup 1/ ..sigma../sub g//sup +/) and cause a local maximum and a deep minimum in the He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) PES, respectively. The crossing with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H/sub 2/(B/sup 1/ ..sigma../sub u//sup +/) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. Coupled-channel equations for rotational and rovibrational energy transfer were solved to obtain partial, integral, and differential cross sections at scattering energies up to 0.210 eV.

Research Organization:
California Univ., Berkeley (USA)
OSTI ID:
7149023
Country of Publication:
United States
Language:
English