Kinetic isotope effects for the reactions of muonic helium and muonium with H2

Donald G. Fleming; Donald J. Arseneau; Oleksandr Sukhorukov; Jess H. Brewer; Steven L. Mielke; George C. Schatz; Bruce C. Garrett; Kirk A. Peterson; Donald G. Truhlar

doi:10.1126/science.1199421

Kinetic isotope effects for the reactions of muonic helium and muonium with H²

Donald G. Fleming, Donald J. Arseneau, Oleksandr Sukhorukov, Jess H. Brewer, Steven L. Mielke, George C. Schatz, Bruce C. Garrett, Kirk A. Peterson, Donald G. Truhlar

Chemistry (Twin Cities)

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

79 Scopus citations

Abstract

The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ∼4.1 atomic mass units (^4.1H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of ^4.1H with ¹H₂ to produce ^4.1H¹H + ¹H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of ^0.11H (where ^0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10^-4 to 10 ^-2 range.

Original language	English (US)
Pages (from-to)	448-450
Number of pages	3
Journal	Science
Volume	331
Issue number	6016
DOIs	https://doi.org/10.1126/science.1199421
State	Published - Jan 28 2011

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Copyright 2011 Elsevier B.V., All rights reserved.

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@article{29f26974536d4a6d9e773968aee8b28b,

title = "Kinetic isotope effects for the reactions of muonic helium and muonium with H2",

abstract = "The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ∼4.1 atomic mass units (4.1H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10 -2 range.",

author = "Fleming, {Donald G.} and Arseneau, {Donald J.} and Oleksandr Sukhorukov and Brewer, {Jess H.} and Mielke, {Steven L.} and Schatz, {George C.} and Garrett, {Bruce C.} and Peterson, {Kirk A.} and Truhlar, {Donald G.}",

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doi = "10.1126/science.1199421",

language = "English (US)",

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TY - JOUR

T1 - Kinetic isotope effects for the reactions of muonic helium and muonium with H2

AU - Fleming, Donald G.

AU - Arseneau, Donald J.

AU - Sukhorukov, Oleksandr

AU - Brewer, Jess H.

AU - Mielke, Steven L.

AU - Schatz, George C.

AU - Garrett, Bruce C.

AU - Peterson, Kirk A.

AU - Truhlar, Donald G.

PY - 2011/1/28

Y1 - 2011/1/28

N2 - The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ∼4.1 atomic mass units (4.1H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10 -2 range.

AB - The neutral muonic helium atom may be regarded as the heaviest isotope of the hydrogen atom, with a mass of ∼4.1 atomic mass units (4.1H), because the negative muon almost perfectly screens one proton charge. We report the reaction rate of 4.1H with 1H2 to produce 4.1H1H + 1H at 295 to 500 kelvin. The experimental rate constants are compared with the predictions of accurate quantum-mechanical dynamics calculations carried out on an accurate Born-Huang potential energy surface and with previously measured rate constants of 0.11H (where 0.11H is shorthand for muonium). Kinetic isotope effects can be compared for the unprecedentedly large mass ratio of 36. The agreement with accurate quantum dynamics is quantitative at 500 kelvin, and variational transition-state theory is used to interpret the extremely low (large inverse) kinetic isotope effects in the 10-4 to 10 -2 range.

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