15min:

VADIM L. STAKHURSKY, XIAOYONG LIU, VLADIMIR A. LOZOVSKY, ILIAS SIOUTIS, C. BRADLEY MOORE, TERRY A. MILLER, Department of Chemistry, The Ohio State University, 120 W. 18th Avenue, Columbus, OH 43210.

Methoxy is a radical ubiquitous in the reactions of combustion and oxidation of hydrocarbon compounds in the atmosphere. Because of its relatively small size and degenerate X²E ground electronic state, it presents a benchmark system for theoreticians to study the multimode Jahn-Teller (JT) effect in the presence of spin-orbit interaction. We have coupled an effective Hamiltonian, including Jahn-Teller coupling terms of up to 3^d order, with a powerful computational engine that allows for quick calculations of spin-vibronic eigenstates and, correspondingly, eigenfunctions from which spectrum intensities can be derived. A graphical user interface, coupled with this computational core, helps to visualize the simulated spectra and compare them with the experimental traces. We simulate and discuss the intensities and spin-vibronic level positions, that we have observed in 4 dispersed fluorescence spectra obtained by pumping the A state vibrational levels 3⁵, 3¹4¹, 3³5¹ and 3³6¹, and complementary data that have been obtained in SEP experiments of Temps and coworkers.