Nonadiabatic Processes Relevant to HEDMs and Atmospheric Chemistry.

摘要

Our research focuses on the electronic structure aspects of electronically non adiabatic processes relevant to the stability and combustion of high energy density materials (HEDMs) and atmospheric chemistry. Our funded research has focused on two problems the reaction of B(P-2) with H2 and reaction O(P-3) + H2O right arrow OH(X(sup 2)II) + OH(A2(sup 2)Sigma(+)). Perhaps the most potentially influential aspect of our research is our work on how the connectivity of points conical intersection impacts nonadiabatic events. In each of these systems unanticipated aspects of the loci of these seams of conical intersection has lead to new avenues of research. In the course of our previous AFOSR funded research we demonstrated that B-H2 exhibits a confluence, an intersection of two branches of same seam of conical intersection, a feature of conical intersections unknown a decade ago. Recently we have shown that confluences can exist not just in tri-atomic molecules but in polyatomic molecules as well and developed an efficient method for locating and characterizing confluences. Our study of the O(P-3) + H2O reaction suggests the existence of an alternative coalescence, a subspace of nuclear coordinate space in which two distinct seam coalesce. While intersections of three states are well known when there is symmetry they appear to be essentially unknown for general polyatomic systems.