Vibrational second-order perturbation theory based on curvilinear coordinates: Thermochemical applications

Abstract

This work improves and extends a general and robust workflow for the computation of anharmonic vibrational frequencies to thermodynamic functions, paving the way toward the study of large flexible molecules. The key new feature is the extension of closed-form expressions for both zero-point vibrational energies and partition functions to second-order vibrational perturbation theory based on curvilinear internal coordinates. The use of curvilinear coordinates enables the reduction of couplings between different degrees of freedom, enriching the arsenal of existing vibrational approaches, and can lead to effective, low-dimensional linear-scaling models. The accuracy of the results obtained for some prototypical systems paves the way toward the systematic use of this new implementation in the study of molecules containing a few dozen atoms, as exemplified by the test cases of a molecular motor, a nucleoside, and two hormones.