Quantum dynamics calculations on isotope effects of hydrogen transfer isomerization in formic acid dimer

Abstract

We present a quantum dynamics study on the isotope effects of hydrogen transfer isomerization in the formic acid dimer, and this is achieved by multidimensional dynamics calculations with an efficient quantum mechanical theoretical scheme developed by our group, on a full-dimensional neural network ab initio potential energy surface. The ground-state and fundamental tunneling splittings for four deuterium isotopologues of formic acid dimer are considered, and the calculated results are in very good general agreement with the available experimental measurements. Strong isotope effects are revealed, the mode-specific fundamental excitation effects on the tunneling rate are evidently influenced by the deuterium substitution of H atom with the substitution on the OH bond being more effective than on the CH bond. Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen transfer processes.