Quantum vibration perturbation approach with polyatomic probe in simulating infrared spectra
Cong, Y (Cong, Yang); Zhai, Y (Zhai, Yu); Yang, JT (Yang, Jitai); Grofe, A (Grofe, Adam); Gao, JL (Gao, Jiali); Li, H (Li, Hui)
Physical Chemistry Chemical Physics, 2022, Volume 24, pp. 1174-1182.
The quantitative prediction of vibrational spectra of chromophore molecules in solution is challenging and numerous methods have been developed. In this work, we present a quantum vibration perturbation (QVP) approach, which is a procedure that combines molecular quantum vibration and molecular dynamics with perturbation theory. In this framework, an initial Newtonian molecular dynamics simulation is performed, followed by a substitution process to embed molecular quantum vibrational wave functions into the trajectory. The instantaneous vibrational frequency shift at each time step is calculated using the Rayleigh-Schrodinger perturbation theory, where the perturbation operator is the difference in the vibrational potential between the reference chromophore and the perturbed chromophore in the environment. Semi-classical statistical mechanics is employed to obtain the spectral lineshape function. We validated our method using HCOOH center dot nH(2)O (n = 1-2) clusters and HCOOH aqueous solution as examples. The QVP method can be employed for rapid prediction of the vibrational spectrum of a specific mode in solution.
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