Accurate ab Initio Thermal Rate Constants for Reaction of O(P-3) with H-2 and Isotopic Analogues

作者：Thanh Lam Nguyen; Stanton John F^*

来源：Journal of Physical Chemistry A, 2014, 118(27): 4918-4928.

DOI：10.1021/jp5037124

Semiclassical transition state theory, in combination with high accuracy quantum chemistry, is used to compute thermal rate constants from first principles for the O(P-3) + H-2 reaction and its isotopic counterparts. In the temperature regime of 298-3500 K (which spans 8 orders of magnitude for rate constants), our theoretical results are in excellent agreement (within 5-15%) with all available experimental data from 298 to 2500 K but are somewhat too low (from 15 to 35%) at higher temperatures. Several possible reasons that might cause the degradation at high temperatures are discussed. Vibrational state-selected rate constants and their correlations with normal thermal rate constant are derived and are given in the Supporting Information.

• 出版日期2014-7-10