Calculations of kinetic isotope effects (KIEs) provide challenging tests of quantal mass effects on reaction rates, and muonium KIEs are the most challenging. Here, we show that it can be very important to include reaction-coordinate-dependent vibrational anharmonicity along the whole reaction path to calculate tunneling probabilities and KIEs. For the reaction of propane with Mu, this decreases both the height and width of the vibrationally adiabatic potential barrier, with both effects increasing the rate constants. Our results agree well with the experimental observations.
Bibliographical noteFunding Information:
This work was supported in part by the National Natural Science Foundation of China (21973053 and 91841301) and by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award DE-SC0015997.
PubMed: MeSH publication types
- Journal Article