Investigating Tunneling Controlled Reactions with Ring Polymer Molecular Dynamics

Here we present an ab-initio on-the-fly rate constant computation on the decay of methylhydroxycarbene with Ring polymer molecular dynamics (RPMD). Experiments show that hydroxycarbenes can decay rapidly through a high but thin barrier instead of a lower but broader barrier at 11 K. We investigate the tunneling of the transferring proton with RPMD which can accurately describe nuclear quantum effects. Quantum free energy profiles and transmission coefficients are computed in order to construct the full rate constants. We compute RPMD reaction rates at various temperatures which agree with previous experiments and theoretical studies.