DYNAMICAL ANALYSIS OF HIGHLY EXCITED MOLECULAR SPECTRA

Kellman, Michael E.

University of Oregon

关键词: Acetylene;    Combustion;    Highly Excited Vibrations;    37 Inorganic, Organic, Physical And Analytical Chemistry;    Bifurcation;   

DOI  :  10.2172/842017
RP-ID  :  234020
RP-ID  :  FG03-98ER14848
RP-ID  :  842017

美国|英语

来源: UNT Digital Library

【 摘 要 】

Spectra and internal dynamics of highly excited molecules are essential to understanding processes of fundamental importance for combustion, including intramolecular energy transfer and isomerization reactions. The goal of our program is to develop new theoretical tools to unravel information about intramolecular dynamics encoded in highly excited experimental spectra. We want to understand the formations of ''new vibrational modes'' when the ordinary normal modes picture breaks down in highly excited vibrations. We use bifurcation analysis of semiclassical versions of the effective Hamiltonians used by spectroscopists to fit complex experimental spectra. Specific molecular systems are of interest for their relevance to combustion and the availability of high-quality experimental data. Because of its immense importance in combustion, the isomerizing acetylene/vinylidene system has been the object of long-standing experimental and theoretical research. We have made significant progress in systematically understanding the bending dynamics of the acetylene system. We have begun to make progress on extending our methodology to the full bend-stretch vibrational degrees of freedom, including dynamics with multiple wells and above barrier motion, and time-dependent dynamics. For this, development of our previous methods using spectroscopic fitting Hamiltonians is needed, for example, for systems with multiple barriers.