DOI: 10.1063/1.1670716. Correlation of Experimental Rate Constants of the Hydrogen Exchange Reactions with a Theoretical H3 Potential Surface, Using Transition-State Theory

Correlation of Experimental Rate Constants of the Hydrogen Exchange Reactions with a Theoretical H3 Potential Surface, Using Transition-State Theory

10.1063/1.1670716

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The recent ab initio potential surface for H3 obtained by Shavitt, Stevens, Minn, and Karplus is used with one empirical parameter, a uniform scale factor for the energy profile along the reaction path, to compute rate constants for various isotopic forms of the H+H2 exchange reaction. The scale factor is adjusted to give agreement with the high-temperature part of the experimental rates recently measured by Westenberg and de Haas, and the results are compared with all the available experimental data. Tunneling is estimated by fitting a one-dimensional Eckart barrier to the higher 30% of the computed reaction-path barrier. It is concluded that the ab initio barrier needs to be scaled down by only 11% in order to reproduce the best experimental data, and the “experimental” barrier height is accordingly obtained as 9.8 ± 0.2 kcal/mole.

Bibliography

Shavitt, I. (1968). Correlation of Experimental Rate Constants of the Hydrogen Exchange Reactions with a Theoretical H3 Potential Surface, Using Transition-State Theory. The Journal of Chemical Physics, 49(9), 4048â4056.

Authors 1

Isaiah Shavitt (first)

References 40 Referenced 102

10.1063/1.1730599 / J. Chem. Phys. (1959)
10.1038/1781207a0 / Nature (1956)
{'key': '2024020904240441500_r2a'}
{'key': '2024020904240441500_r3'}
10.1139/v64-364 / Can. J. Chem. (1964)
10.1063/1.1695853 / J. Chem. Phys. (1965)
10.1063/1.1727235 / J. Chem. Phys. (1966)
10.1039/df9674400092 / Discussions Faraday Soc. (1967)
10.1063/1.1712093 / J. Chem. Phys. (1967)
{'key': '2024020904240441500_r9'}
10.1063/1.1696050 / J. Chem. Phys. (1965)
10.1063/1.1727841 / J. Chem. Phys. (1966)
10.1063/1.1669809 / J. Chem. Phys. (1968)
10.1063/1.1695879 / J. Chem. Phys. (1965)
10.1063/1.1712057 / J. Chem. Phys. (1967)
10.1063/1.1701559 / J. Chem. Phys. (1967)
10.1063/1.1669504 / J. Chem. Phys. (1968)
10.1021/ja01462a001 / J. Am. Chem. Soc. (1961)
10.1103/PhysRev.35.1303 / Phys. Rev. (1930)
10.1063/1.1730545 / J. Chem. Phys. (1959)
10.1063/1.1732373 / J. Chem. Phys. (1962)
10.1063/1.1733529 / J. Chem. Phys. (1963)
10.1063/1.1695977 / J. Chem. Phys. (1965)
10.1063/1.1696178 / J. Chem. Phys. (1965)
10.1039/tf9686400371 / Trans. Faraday Soc. (1968)
10.1039/tf9595500001 / Trans. Faraday Soc. (1959)
10.1039/df9674400163 / Discussions Faraday Soc. (1967)
{'key': '2024020904240441500_r22', 'first-page': '1140', 'volume': '89', 'year': '1953', 'journal-title': 'Phys. Rev.'} / Phys. Rev. (1953)
{'key': '2024020904240441500_r23'}
{'key': '2024020904240441500_r24', 'first-page': '782', 'volume': '36', 'year': '1930', 'journal-title': 'Z. Elektrochem.'} / Z. Elektrochem. (1930)
{'key': '2024020904240441500_r24a', 'first-page': '419', 'volume': 'B10', 'year': '1930', 'journal-title': 'Z. Physik. Chem.'} / Z. Physik. Chem. (1930)
{'key': '2024020904240441500_r25', 'first-page': '124', 'volume': 'A152', 'year': '1935', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1935)
10.1063/1.1742610 / J. Chem. Phys. (1956)
10.1002/bscb.19510600111 / Bull. Soc. Chim. Belges (1951)
{'key': '2024020904240441500_r28'}
10.1063/1.1731203 / J. Chem. Phys. (1960)
10.6028/jres.041.037 / J. Res. Natl. Bur. Std. (1948)
10.1139/p57-079 / Can. J. Phys. (1957)
10.1139/p59-070 / Can. J. Phys. (1959)
{'key': '2024020904240441500_r33', 'first-page': '482', 'volume': '5', 'year': '1960', 'journal-title': 'J. Mol. Spectry.'} / J. Mol. Spectry. (1960)

Dates

Type	When
Created	21 years, 6 months ago (Feb. 6, 2004, 2:22 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 11:24 p.m.)
Indexed	1 year, 6 months ago (Feb. 10, 2024, 11:51 a.m.)
Issued	56 years, 9 months ago (Nov. 1, 1968)
Published	56 years, 9 months ago (Nov. 1, 1968)
Published Print	56 years, 9 months ago (Nov. 1, 1968)

Funders 0

None

BibTeX

@article{Shavitt_1968, title={Correlation of Experimental Rate Constants of the Hydrogen Exchange Reactions with a Theoretical H3 Potential Surface, Using Transition-State Theory}, volume={49}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1670716}, DOI={10.1063/1.1670716}, number={9}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Shavitt, Isaiah}, year={1968}, month=nov, pages={4048–4056} }

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