Comparative Analysis of Uncoupled Mode Approximations for Molecular Thermochemistry and Kinetics.

Abstract

The accurate prediction of thermochemistry and kinetic parameters is an important task for reaction modeling. Unfortunately, the commonly used harmonic oscillator model is often not accurate enough due to the absence of anharmonic effects. In this work, we improve the representation of an anharmonic potential energy surface (PES) using uncoupled mode (UM) approximations, which model the full-dimensional PES as a sum of one-dimensional potentials of each mode. We systematically analyze different PES sampling schemes and coordinate systems for constructing the one-dimensional potentials, and benchmark the performance of UM methods on data sets of molecular thermochemistry and kinetic properties. The results show that the accuracy of the UM approach strongly depends on how the one-dimensional potentials are defined. If one-dimensional potentials are constructed by sampling along normal mode directions (UM-N) or along the directions that minimize intermode coupling (E- and E'-optimized), the accuracies of the predicted properties are not significantly improved compared to the harmonic oscillator model. However, significant improvements can be achieved by sampling the torsional modes separately from the vibrational modes (UM-T and UM-VT). In this work, three types of coordinate systems are examined, including redundant internal coordinates (RIC), hybrid internal coordinates (HIC), and translation-rotation-internal coordinates (TRIC). The HIC and TRIC coordinate systems can outperform RIC since transition state species may contain large-amplitude interfragmentary motions that regular internal coordinates can not describe adequately. Among all the methods we examined, the activation energies and pre-exponential factors calculated using UM-VT with either TRIC or HIC best agree with the reference values. Since UM-VT requires only a number of additional single point energy calculations for each independent mode, the scaling of computational costs of UM-VT is the same as that of the standard harmonic oscillator model, making UM-VT an appealing way of calculating the thermochemistry and kinetic properties for large-size systems.