Investigating Tunneling-Controlled Chemical Reactions through Ab Initio Ring Polymer Molecular Dynamics

We use the ab initio ring polymer molecular dynamics (RPMD) approach to investigate tunneling-controlled reactions in methylhydroxycarbene. Nuclear tunneling effects enable molecules to overcome the barriers which cannot be overcome classically. Under low-temperature conditions, intrinsic quantum tunneling effects can facilitate the chemical reaction in a pathway that is favored neither thermodynamically nor kinetically. This behavior is referred to as the tunneling-controlled chemical reaction and is regarded as the third paradigm of chemical reaction controls. In this work, we use the ab initio RPMD approach to incorporate the tunneling effects in our quantum dynamics simulations and investigate the reaction kinetics of two competitive reaction pathways at various temperatures. The reaction rate constants obtained here agree extremely well with the experimentally measured rates. We demonstrate the feasibility of using ab initio RPMD rate calculations in a realistic molecular system and provide an interesting and important example for future investigations of reaction mechanisms dominated by quantum tunneling effects.

Automated summary

The ab initio RPMD approach was used to investigate tunneling-controlled reactions in methylhydroxycarbene, showing that nuclear tunneling effects can facilitate chemical reactions under low-temperature conditions, leading to the concept of tunneling-controlled chemical reactions as the third paradigm. The reaction kinetics of two competitive pathways were studied at various temperatures, with the obtained reaction rate constants matching well with experimental rates, demonstrating the feasibility of using ab initio RPMD rate calculations in realistic molecular systems for investigating reaction mechanisms dominated by quantum tunneling effects.