Full- and reduced-dimensionality instanton calculations of the tunnelling splitting in the formic acid dimer.

Abstract

The ring-polymer instanton approach is applied to compute the ground-state tunnelling splitting of four isotopomers of the formic acid dimer using the accurate PES of Qu and Bowman [Phys. Chem. Chem. Phys., 2016, 18, 24835]. As well as performing the calculations in full dimensionality, we apply a reduced-dimensionality approach to study how the results converge as successively more degrees of freedom are included. The instanton approximation compares well to exact quantum results where they are available but shows that nearly all the modes are required to quantitatively obtain the tunnelling splitting. The full-dimensional instanton calculation reproduces the experimental results, with an error of only about 20 percent.