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

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.