ANALYTICAL POTENTIAL ENERGY SURFACE FOR THE NH3+H[--]NH2+H-2 REACTION - APPLICATION OF VARIATIONAL TRANSITION-STATE THEORY AND ANALYSIS OF THE EQUILIBRIUM CONSTANTS AND KINETIC ISOTOPE EFFECTS USING CURVILINEAR AND RECTILINEAR COORDINATES

摘要

The potential energy surface (PES) for the gas-phase NH3+H<->NH2+H-2 reaction is constructed with suitable functional forms to represent the stretching and bending modes, and using as calibration criterion the reactant and product experimental properties and the ab initio saddle point properties. This surface is then used to calculate rate constants with variational transition-state theory over the temperature range 300-2000 K. While the forward rate constants agree with experimental results, the reverse ones are lower by factors of between 4 and 6. Since the same PES is used and these rates are related by detailed balance, this disagreement could indicate an uncertainty in the few available experimental studies for the reverse reaction. We also provide a detailed analysis of the equilibrium constants and of the kinetic isotope effects and compare the results of this analytical PES with earlier ab initio reaction-path calculations. Finally, for the vibrational frequency calculations, we analyze the consequences of the choice of different coordinate systems (curvilinear or rectilinear) on Various kinetic magnitudes. (C) 1997 American Institute of Physics. [References: 44]