Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

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

doi:10.1063/1.3657440

Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

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

Chemistry (Twin Cities)

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

33 Scopus citations

Abstract

The neutral muonic helium atom ⁴Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of ⁴Heμ with molecular hydrogen, ⁴Heμ + H₂ → ⁴HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, k_Heμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for k_Heμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for k_Heμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H₂ and Mu + H₂ reactions in a novel study of kinetic isotope effects for the H + H₂ reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

Original language	English (US)
Article number	184310
Journal	Journal of Chemical Physics
Volume	135
Issue number	18
DOIs	https://doi.org/10.1063/1.3657440
State	Published - Nov 14 2011

Bibliographical note

Funding Information:
We thank Dr. Syd Kreitzman for his management of the CMMS Facility and for the technical support it provides. A special thanks is given to Neil Aucoin for his engineering input and design of the heater for the target cell used in these experiments. We gratefully acknowledge NSERC for its financial support of this research. The work at Pacific Northwest National Laboratory (PNNL) was supported by the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Science, U.S. Department of Energy (DOE). Battelle operates PNNL for DOE. The work at the University of Minnesota was supported in part by the DOE under Grant No. DE-FG02-86ER13579. The work at Northwestern was supported by AFOSR grant FA9550-10-1-0205.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Publisher link

10.1063/1.3657440

Find It

Find It at U of M Libraries

Fingerprint

Dive into the research topics of 'Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass'. Together they form a unique fingerprint.

Cite this

Fleming, D. G., Arseneau, D. J., Sukhorukov, O., Brewer, J. H., Mielke, S. L., Truhlar, D. G., Schatz, G. C., Garrett, B. C., & Peterson, K. A. (2011). Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass. Journal of Chemical Physics, 135(18), Article 184310. https://doi.org/10.1063/1.3657440

Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass. / Fleming, Donald G.; Arseneau, Donald J.; Sukhorukov, Oleksandr et al.
In: Journal of Chemical Physics, Vol. 135, No. 18, 184310, 14.11.2011.

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

Fleming, DG, Arseneau, DJ, Sukhorukov, O, Brewer, JH, Mielke, SL, Truhlar, DG, Schatz, GC, Garrett, BC & Peterson, KA 2011, 'Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass', Journal of Chemical Physics, vol. 135, no. 18, 184310. https://doi.org/10.1063/1.3657440

Fleming DG, Arseneau DJ, Sukhorukov O, Brewer JH, Mielke SL, Truhlar DG et al. Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass. Journal of Chemical Physics. 2011 Nov 14;135(18):184310. doi: 10.1063/1.3657440

Fleming, Donald G. ; Arseneau, Donald J. ; Sukhorukov, Oleksandr et al. / Kinetics of the reaction of the heaviest hydrogen atom with H₂, the ⁴Heμ + H₂ → ⁴HeμH + H reaction : Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass. In: Journal of Chemical Physics. 2011 ; Vol. 135, No. 18.

@article{fe840e9078a74bd5bd28b0e591cc8120,

title = "Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction: Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass",

abstract = "The neutral muonic helium atom 4Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, kHeμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for kHeμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for kHeμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.",

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

note = "Funding Information: We thank Dr. Syd Kreitzman for his management of the CMMS Facility and for the technical support it provides. A special thanks is given to Neil Aucoin for his engineering input and design of the heater for the target cell used in these experiments. We gratefully acknowledge NSERC for its financial support of this research. The work at Pacific Northwest National Laboratory (PNNL) was supported by the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Science, U.S. Department of Energy (DOE). Battelle operates PNNL for DOE. The work at the University of Minnesota was supported in part by the DOE under Grant No. DE-FG02-86ER13579. The work at Northwestern was supported by AFOSR grant FA9550-10-1-0205.",

year = "2011",

month = nov,

day = "14",

doi = "10.1063/1.3657440",

language = "English (US)",

volume = "135",

journal = "Journal of Chemical Physics",

issn = "0021-9606",

publisher = "American Institute of Physics",

number = "18",

}

TY - JOUR

T1 - Kinetics of the reaction of the heaviest hydrogen atom with H2, the 4Heμ + H2 → 4HeμH + H reaction

T2 - Experiments, accurate quantal calculations, and variational transition state theory, including kinetic isotope effects for a factor of 36.1 in isotopic mass

AU - Fleming, Donald G.

AU - Arseneau, Donald J.

AU - Sukhorukov, Oleksandr

AU - Brewer, Jess H.

AU - Mielke, Steven L.

AU - Truhlar, Donald G.

AU - Schatz, George C.

AU - Garrett, Bruce C.

AU - Peterson, Kirk A.

N1 - Funding Information: We thank Dr. Syd Kreitzman for his management of the CMMS Facility and for the technical support it provides. A special thanks is given to Neil Aucoin for his engineering input and design of the heater for the target cell used in these experiments. We gratefully acknowledge NSERC for its financial support of this research. The work at Pacific Northwest National Laboratory (PNNL) was supported by the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Science, U.S. Department of Energy (DOE). Battelle operates PNNL for DOE. The work at the University of Minnesota was supported in part by the DOE under Grant No. DE-FG02-86ER13579. The work at Northwestern was supported by AFOSR grant FA9550-10-1-0205.

PY - 2011/11/14

Y1 - 2011/11/14

N2 - The neutral muonic helium atom 4Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, kHeμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for kHeμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for kHeμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

AB - The neutral muonic helium atom 4Heμ, in which one of the electrons of He is replaced by a negative muon, may be effectively regarded as the heaviest isotope of the hydrogen atom, with a mass of 4.115 amu. We report details of the first muon spin rotation (μSR) measurements of the chemical reaction rate constant of 4Heμ with molecular hydrogen, 4Heμ + H2 → 4HeμH + H, at temperatures of 295.5, 405, and 500 K, as well as a μSR measurement of the hyperfine coupling constant of muonic He at high pressures. The experimental rate constants, kHeμ, are compared with the predictions of accurate quantum mechanical (QM) dynamics calculations carried out on a well converged Born-Huang (BH) potential energy surface, based on complete configuration interaction calculations and including a Born-Oppenheimer diagonal correction. At the two highest measured temperatures the agreement between the quantum theory and experiment is good to excellent, well within experimental uncertainties that include an estimate of possible systematic error, but at 295.5 K the quantum calculations for kHeμ are below the experimental value by 2.1 times the experimental uncertainty estimates. Possible reasons for this discrepancy are discussed. Variational transition state theory calculations with multidimensional tunneling have also been carried out for kHeμ on the BH surface, and they agree with the accurate QM rate constants to within 30% over a wider temperature range of 200-1000 K. Comparisons between theory and experiment are also presented for the rate constants for both the D + H2 and Mu + H2 reactions in a novel study of kinetic isotope effects for the H + H2 reactions over a factor of 36.1 in isotopic mass of the atomic reactant.

UR - http://www.scopus.com/inward/record.url?scp=81155138813&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=81155138813&partnerID=8YFLogxK

U2 - 10.1063/1.3657440

DO - 10.1063/1.3657440

M3 - Article

C2 - 22088068

AN - SCOPUS:81155138813

SN - 0021-9606

VL - 135

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 18

M1 - 184310

ER -