Vibrational second-order perturbation theory based on curvilinear coordinates: Thermochemical applications
Year: 2025
Type: article
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.
Source: The Journal of Chemical Physics
DOI: 10.1063/5.0252006
Authors: M. Mendolicchio, V. Barone
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $3,500
OpenAlex ID: W4409623872