Dynamics Calculations of the Flexibility and Vibrational Spectrum of the Linear Alkane C14H30, Based on Machine-Learned Potentials

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2024-12, Vol.128 (49), p.10713-10722
• Main Authors: Qu, Chen, Houston, Paul L., Conte, Riccardo, Bowman, Joel M.
• Format: Article
• Language: English
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c06943

Hydrocarbons are the central feedstock of fuels, solvents, lubricants, and the starting materials for many synthetic materials, and thus the physical properties of hydrocarbons have received intense study. Among these, the molecular flexibility and the power and infrared spectroscopies are the focus of this paper. These are examined for the linear alkane C14H30 using molecular dynamics (MD) calculations and recent machine-learned potentials. All MD calculations are microcanonical and start at the global linear minimum. The radius of gyration, the number of gauche bond conformations and the distributions of all C–C distances are reported as a function of the total internal energy and as a function of time. These are compared to the power spectra and to the double harmonic spectra of stationary points. Spectral features of the double harmonic spectra smoothly track structural differences, measured by the number of gauche conformations in the molecule. Preliminary calculations using the quantum local mode model for the CH-stretch are presented and satisfactorily capture anharmonic effects.