### Abstract

We study the collinear H + FH → HF + H and D + FD → DF + D reactions on a potential-energy surface that has twin 1.75 kcal/mol saddle points. We present accurate quantal reaction probabilities over a wide energy range, including three resonance energies and three resonance widths for each isotopic case. From these we calculate accurate quantal rate constants at temperatures 75-7000 K for H + FH and 75-2400 K for D + FD; and we separate out the contributions of the lowest-energy resonance to the low-temperature rates. We present plots of S-matrix phases and eigenphases and Argand diagrams. The accurate quantal results are used to test a wide variety of approximate dynamical results: semiclassical and quantal resonance calculations based on the vibrationally adiabatic model; rate constants calculated by conventional transition-state theory, three versions of variational transition-state theory, and the unified statistical model; and vibrationally adiabatic transmission coefficients.

Original language | English |
---|---|

Pages (from-to) | 3806-3817 |

Number of pages | 12 |

Journal | Journal of Physical Chemistry |

Volume | 85 |

Issue number | 25 |

Publication status | Published - 1981 |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

*Journal of Physical Chemistry*,

*85*(25), 3806-3817.

**Reaction probabilities, resonances, and thermal rate constants for the collinear reactions H + FH and D + FD on a low-barrier surface. Close-coupling and tunneling calculations, variational transition-state theory, and the unified statistical model.** / Garrett, Bruce C.; Truhlar, Donald G.; Grev, Roger S.; Schatz, George C; Walker, Robert B.

Research output: Contribution to journal › Article

*Journal of Physical Chemistry*, vol. 85, no. 25, pp. 3806-3817.

}

TY - JOUR

T1 - Reaction probabilities, resonances, and thermal rate constants for the collinear reactions H + FH and D + FD on a low-barrier surface. Close-coupling and tunneling calculations, variational transition-state theory, and the unified statistical model

AU - Garrett, Bruce C.

AU - Truhlar, Donald G.

AU - Grev, Roger S.

AU - Schatz, George C

AU - Walker, Robert B.

PY - 1981

Y1 - 1981

N2 - We study the collinear H + FH → HF + H and D + FD → DF + D reactions on a potential-energy surface that has twin 1.75 kcal/mol saddle points. We present accurate quantal reaction probabilities over a wide energy range, including three resonance energies and three resonance widths for each isotopic case. From these we calculate accurate quantal rate constants at temperatures 75-7000 K for H + FH and 75-2400 K for D + FD; and we separate out the contributions of the lowest-energy resonance to the low-temperature rates. We present plots of S-matrix phases and eigenphases and Argand diagrams. The accurate quantal results are used to test a wide variety of approximate dynamical results: semiclassical and quantal resonance calculations based on the vibrationally adiabatic model; rate constants calculated by conventional transition-state theory, three versions of variational transition-state theory, and the unified statistical model; and vibrationally adiabatic transmission coefficients.

AB - We study the collinear H + FH → HF + H and D + FD → DF + D reactions on a potential-energy surface that has twin 1.75 kcal/mol saddle points. We present accurate quantal reaction probabilities over a wide energy range, including three resonance energies and three resonance widths for each isotopic case. From these we calculate accurate quantal rate constants at temperatures 75-7000 K for H + FH and 75-2400 K for D + FD; and we separate out the contributions of the lowest-energy resonance to the low-temperature rates. We present plots of S-matrix phases and eigenphases and Argand diagrams. The accurate quantal results are used to test a wide variety of approximate dynamical results: semiclassical and quantal resonance calculations based on the vibrationally adiabatic model; rate constants calculated by conventional transition-state theory, three versions of variational transition-state theory, and the unified statistical model; and vibrationally adiabatic transmission coefficients.

UR - http://www.scopus.com/inward/record.url?scp=33845556714&partnerID=8YFLogxK

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M3 - Article

AN - SCOPUS:33845556714

VL - 85

SP - 3806

EP - 3817

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 25

ER -