### Abstract

We present a new potential energy surface (called G3) for the chemical reaction Cl + H_{2} → HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with least-action ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data.

Original language | English (US) |
---|---|

Pages (from-to) | 13575-13587 |

Number of pages | 13 |

Journal | Journal of Physical Chemistry |

Volume | 100 |

Issue number | 32 |

State | Published - Aug 8 1996 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Engineering(all)
- Physical and Theoretical Chemistry

### Cite this

_{2}Cl system and its use for calculations of rate coefficients and kinetic isotope effects.

*Journal of Physical Chemistry*,

*100*(32), 13575-13587.

**An improved potential energy surface for the H _{2}Cl system and its use for calculations of rate coefficients and kinetic isotope effects.** / Allison, Thomas C.; Lynch, Gillian C.; Truhlar, Donald G.; Gordon, Mark S.

Research output: Contribution to journal › Article

_{2}Cl system and its use for calculations of rate coefficients and kinetic isotope effects',

*Journal of Physical Chemistry*, vol. 100, no. 32, pp. 13575-13587.

_{2}Cl system and its use for calculations of rate coefficients and kinetic isotope effects. Journal of Physical Chemistry. 1996 Aug 8;100(32):13575-13587.

}

TY - JOUR

T1 - An improved potential energy surface for the H2Cl system and its use for calculations of rate coefficients and kinetic isotope effects

AU - Allison, Thomas C.

AU - Lynch, Gillian C.

AU - Truhlar, Donald G.

AU - Gordon, Mark S.

PY - 1996/8/8

Y1 - 1996/8/8

N2 - We present a new potential energy surface (called G3) for the chemical reaction Cl + H2 → HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with least-action ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data.

AB - We present a new potential energy surface (called G3) for the chemical reaction Cl + H2 → HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with least-action ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data.

UR - http://www.scopus.com/inward/record.url?scp=0030219446&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0030219446&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0030219446

VL - 100

SP - 13575

EP - 13587

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 32

ER -