화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.98, No.38, 9558-9564, 1994
Direct Ab-Initio Dynamics Calculations of Thermal Rate Constants and Kinetic Isotope Effects for the H+h2O(--)Oh+h-2 Reaction
We present an application of our previously proposed direct ab initio dynamics method for calculating the thermal rate constants and kinetic isotope effects (KIEs) of the H + H2O <-- --> OH + H-2 reaction. Dynamical calculations were based on a full canonical variational transition-state theory plus multidimensional semiclassical tunneling corrections. The minimum energy path (MEP) and Hessians at selected points along this path were calculated at the QCISD/6-311+G(d,p) level of theory. The classical potential energy along the MEP was further improved by a series of single-point PMP4/6-311++G(2df,2pd) calculations. The predicted rate constants and KIEs are in excellent agreement with experimental data for the temperature range from 250 to 2000 K. The accuracy of the Schatz-Elgersma analytical potential energy function for this reaction has also been examined.