Coupled Cluster Semiclassical Estimates of Experimental Reaction Rates: The Interconversion of Glycine Conformer VIp to Ip

We apply the full-dimensional Semiclassical Transition State Theory (SCTST) to estimate the rate constant of glycine molecule interconversion between the VIp and Ip conformers. We have reached an electronic structure accuracy up to the explicitly correlated Coupled Cluster method (CCSD­(T)-F12b/cc-pVDZ-F12) thanks to our parallel implementation. The reaction has been experimentally investigated in the literature and is known to proceed by quantum mechanical tunneling. The SCTST rates improve over other theoretical methods, and our results align with the experimental measurements, thus confirming the accuracy of the fully coupled anharmonic semiclassical tunneling treatment, providing that the level of electronic structure theory gives a reliable estimate of the reaction barrier height and shape. The comparison with experimental half-life times supports the validity of SCTST for glycine VIp–Ip conformer conversion in the cryogenic temperature range, where this theory is usually not considered applicable due to the onset of the deep tunneling regime.