Large anharmonic effects on tunneling and kinetics: Reaction of propane with muonium

Lu Gem Gao; Donald G. Fleming; Donald G. Truhlar; Xuefei Xu

doi:10.1021/acs.jpclett.1c01229

Large anharmonic effects on tunneling and kinetics: Reaction of propane with muonium

Lu Gem Gao, Donald G. Fleming, Donald G. Truhlar, Xuefei Xu

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	4154-4159
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	12
Issue number	17
DOIs	https://doi.org/10.1021/acs.jpclett.1c01229
State	Published - May 6 2021

Bibliographical note

Funding 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.

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title = "Large anharmonic effects on tunneling and kinetics: Reaction of propane with muonium",

abstract = "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.",

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month = may,

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doi = "10.1021/acs.jpclett.1c01229",

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T1 - Large anharmonic effects on tunneling and kinetics

T2 - Reaction of propane with muonium

AU - Gao, Lu Gem

AU - Fleming, Donald G.

AU - Truhlar, Donald G.

AU - Xu, Xuefei

N1 - Funding 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. Publisher Copyright: ©

PY - 2021/5/6

Y1 - 2021/5/6

N2 - 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.

AB - 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.

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Large anharmonic effects on tunneling and kinetics: Reaction of propane with muonium

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