### Abstract

We present accurate quantal rate constants for the D + H_{2} system in the 167-900 K temperature range and rate constants calculated in the separable rotation approximation up to 1500 K. We have calculated rate constants for the three most accurate ab initio potential energy surfaces. The separable-rotation calculations agree to within 2.2% with the present accurate quantal calculations, and the results show substantially better agreement with high-temperature experimental rate constants than do previous quantal calculations. The ab initio rate constants for the LSTH and DMBE surfaces agree well with experiment over a wide temperature range but the newer BKMP surface gives poor agreement at low temperatures. From 200 to 900 K, a factor of 4.5 in temperature, the present totally ab initio reaction rate constants agree with experiment within 13% or better at each temperature, with an average absolute deviation of only 5%.

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

Pages (from-to) | 8000-8008 |

Number of pages | 9 |

Journal | Journal of Physical Chemistry |

Volume | 98 |

Issue number | 33 |

State | Published - 1994 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

*Journal of Physical Chemistry*,

*98*(33), 8000-8008.

**Ab Initio chemical kinetics : Converged quantal reaction rate constants for the D + H2 system.** / Mielke, Steven L.; Lynch, Gillian C.; Truhlar, Donald G.; Schwenke, David W.

Research output: Contribution to journal › Article

*Journal of Physical Chemistry*, vol. 98, no. 33, pp. 8000-8008.

}

TY - JOUR

T1 - Ab Initio chemical kinetics

T2 - Converged quantal reaction rate constants for the D + H2 system

AU - Mielke, Steven L.

AU - Lynch, Gillian C.

AU - Truhlar, Donald G.

AU - Schwenke, David W.

PY - 1994

Y1 - 1994

N2 - We present accurate quantal rate constants for the D + H2 system in the 167-900 K temperature range and rate constants calculated in the separable rotation approximation up to 1500 K. We have calculated rate constants for the three most accurate ab initio potential energy surfaces. The separable-rotation calculations agree to within 2.2% with the present accurate quantal calculations, and the results show substantially better agreement with high-temperature experimental rate constants than do previous quantal calculations. The ab initio rate constants for the LSTH and DMBE surfaces agree well with experiment over a wide temperature range but the newer BKMP surface gives poor agreement at low temperatures. From 200 to 900 K, a factor of 4.5 in temperature, the present totally ab initio reaction rate constants agree with experiment within 13% or better at each temperature, with an average absolute deviation of only 5%.

AB - We present accurate quantal rate constants for the D + H2 system in the 167-900 K temperature range and rate constants calculated in the separable rotation approximation up to 1500 K. We have calculated rate constants for the three most accurate ab initio potential energy surfaces. The separable-rotation calculations agree to within 2.2% with the present accurate quantal calculations, and the results show substantially better agreement with high-temperature experimental rate constants than do previous quantal calculations. The ab initio rate constants for the LSTH and DMBE surfaces agree well with experiment over a wide temperature range but the newer BKMP surface gives poor agreement at low temperatures. From 200 to 900 K, a factor of 4.5 in temperature, the present totally ab initio reaction rate constants agree with experiment within 13% or better at each temperature, with an average absolute deviation of only 5%.

UR - http://www.scopus.com/inward/record.url?scp=33645439140&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33645439140&partnerID=8YFLogxK

M3 - Article

VL - 98

SP - 8000

EP - 8008

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 33

ER -