ANGULAR-MOMENTUM DEPENDENCE OF VARIATIONAL TRANSITION-STATES FOR SELECTED ASSOCIATION REACTIONS

The total angular momentum dependence of variational transition states for several reactions without a potential energy barrier on the minimum energy path is illustrated. High-pressure thermal rate constants for Li++(CH3)2O→Li+(CH3)2O and Li++H2O→Li+(H2O) from 200 to 1000 K are obtained from flexible transition-state theory (FTST), with potential functions of Coriongiu, Clementi, Pretsch and Simon and of Clementi and Popkie, respectively. For Li+(H2O) the canonically determined rate constants are 20-50% higher than the microcanonically determined ones, and for Li+(CH3)2O ≈ 55% higher. These differences are attributed to the strong dependence of the transition states on total angular momentum. © 1990.