Mapped Interpolation Scheme for Single-Point Energy Corrections in Reaction Rate Calculations and a Critical Evaluation of Dual-Level Reaction Path Dynamics Methods
暂无分享,去创建一个
Three procedures for incorporating higher level electronic structure data into reaction path dynamics calculations are tested. In one procedure, variational transition state theory with interpolated single-point energies, which is denoted VTST-ISPE, a few extra energies calculated with a higher level theory along the lower level reaction path are used to correct the classical energetic profile of the reaction. In the second procedure, denoted variational transition state theory with interpolated optimized corrections (VTST-IOC), which we introduced earlier, higher level corrections to energies, frequencies, and moments of inertia are based on stationary-point geometries reoptimized at a higher level than the reaction path was calculated. The third procedure, called interpolated optimized energies (IOE), is like IOC except it omits the frequency correction. Three hydrogen-transfer reactions, CH3 + H‘H → CH3H‘ + H (R1), OH + H‘H → HOH‘ + H (R2), and OH + H‘CH3 → HOH‘ + CH3 (R3), are used to test and validat...
[1] Michael Baer,et al. Theory of chemical reaction dynamics , 1985 .
[2] Warren J. Hehre,et al. AB INITIO Molecular Orbital Theory , 1986 .
[3] H. Sellers,et al. Theoretical and computational approaches to interface phenomena , 1994 .