The Dynamics of Large-Amplitude Motion in Energized Molecules

Perry, David S.¹ 

[1] Univ. of Akron, OH (United States). Dept. of Chemistry

关键词: molecular vibrations;    large-amplitude motion;    torsion;    separation of degrees of freedom;    vibrational adiabaticity;    conical intersections;   

DOI  :  10.2172/1254647
RP-ID  :  DOE/ER/14151--26
PID  :  OSTI ID: 1254647
Others  :  Other: 3308690175

美国|英语

来源: SciTech Connect

【 摘 要 】

Chemical reactions involve large-amplitude nuclear motion along the reaction coordinate that serves to distinguish reactants from products. Some reactions, such as roaming reactions and reactions proceeding through a loose transition state, involve more than one large-amplitude degree of freedom. Because of the limitation of exact quantum nuclear dynamics to small systems, one must, in general, define the active degrees of freedom and separate them in some way from the other degrees of freedom. In this project, we use large-amplitude motion in bound model systems to investigate the coupling of large-amplitude degrees of freedom to other nuclear degrees of freedom. This approach allows us to use the precision and power of high-resolution molecular spectroscopy to probe the specific coupling mechanisms involved, and to apply the associated theoretical tools. In addition to slit-jet spectra at the University of Akron, the current project period has involved collaboration with Michel Herman and Nathalie Vaeck of the Universit?? Libre de Bruxelles, and with Brant Billinghurst at the Canadian Light Source (CLS).