화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.104, No.31, 7200-7208, 2000
Improved interpolated correction schemes for dual-level direct dynamics calculation
A set of new correction schemes for dual-level variational transition-state theory calculation has been developed. In the new schemes, an intermediate level of theory is employed to better estimate the width of the reaction energy barrier. Then, adjustable parameters are set in the final calculation to reproduce the estimated high-level barrier width in addition to the high-level energy of reaction and barrier height. The new schemes have been tested in the rate constant calculation of H + H2S -> HS + H-2 and OH + CH4 -> H2O + CH3 reactions with potential energy surface information obtained from several low-and high-level ab initio theories. Compared to the previous correction schemes, the dual-level calculation based on the new schemes produced results, in most cases, in significantly better agreement with the reference high-level calculation. The new schemes are expected to predict more accurate rate constants for those reactions in which tunneling effects are important.