Efficient Quantum Mechanical Calculations of Mode-Specific Tunneling Splittings upon Fundamental Excitation in the Dimer of Formic Acid

J Phys Chem A. 2020 Aug 13;124(32):6536-6543. doi: 10.1021/acs.jpca.0c05471. Epub 2020 Jul 29.

Abstract

The formic acid dimer (FAD) is an important benchmark system for understanding the double hydrogen transfer process. Most recently, Zhang et al. measured a few tunneling splittings upon fundamental excitation of FAD precisely (Zhang, Y. et al. J. Chem. Phys. 2017, 146, 244306); however, relevant theoretical studies are very limited. Here, we present a multidimensional quantum dynamics study on mode-specific tunneling splittings upon fundamental excitation in FAD with an efficient theoretical scheme developed by our group in which the process-oriented basis function customization strategy is combined with the preconditioned inexact spectral transform method. Various mode-specific tunneling splittings upon fundamental excitation are systematically calculated, and interesting mode-specific excitation effects on tunneling rate are identified. In particular, the calculated tunneling splittings for the ν22 and ν21 states are in good agreement with experiment, and the remarkable mode-specific suppression effects upon excitation should result from that the antisymmetric vibrational modes hinder the concerted double H-transfer. The present work is helpful to acquire a better understanding of the mode-specific excitation effects on tunneling processes.