REACTION RATES: ACCURATE QUANTUM DYNAMICAL CALCULATIONS FOR POLYATOMIC SYSTEMS

Abstract

Rate constants of chemical reactions can be computed directly: employing flux correlation functions, no scattering calculations are required. If the reaction is direct, the dynamical simulation can be restricted to the vicinity of the reaction barrier. Therefore accurate thermal rate constants and cumulative reaction probabilities can be calculated for rather large systems. Recent calculations have studied systems with up to six atoms, e.g., H + CH 4 → H 2 + CH 3. The calculations provide a full-dimensional quantum description of the reaction process. In the article, an introduction to the theory of flux correlation functions is given. Methods for the efficient computation of accurate thermal rate constants and cumulative reaction probabilities are reviewed. Connections to transition state ideas are highlighted. The multi-configurational time-dependent Hartree (MCTDH) approach, which facilitates efficient multi-dimensional wave packet propagation, is described and its use in reaction rate calculation is discussed. As examples, recent results for the prototypical polyatomic reaction H + CH 4 → H 2 + CH 3 are presented and rotational effects on the reaction rates of H 2 + OH → H + H 2 O , O + HCl → OH + Cl , and H 2 + Cl → H + HCl are discussed.