The definition of reaction coordinates for reaction-path dynamics

Abstract

We present equations for generalized-normal-mode vibrational frequencies in reaction-path calculations based on various sets of coordinates for describing the internal motions of the system in the vicinity of a reaction path. We consider two special cases in detail as examples, in particular three-dimensional atom–diatom collisions with collinear steepest descent paths and reactions of the form CX3+YZ→CX3 Y+Z with reaction paths having C3v symmetry. We then present numerical comparisons of the differences in harmonic reaction-path frequencies for various coordinate choices for three such systems, namely, H+H2→H2+H, O+H2→OH+H, and CH3+H2→CH4+H. We test the importance of the differences in the harmonic frequencies for dynamics calculations by using them to compute thermal rate constants using variational transition state theory with semiclassical ground-state tunneling corrections. We present a new coordinate system for the reaction CH3+H2 that should allow for more accurate calculations than the Cartesian system used for previous reaction-path calculations on this and other polyatomic systems.