## Abstract

The state-selected reaction rates OH(n_{OH} = 0,1) + H _{2}(n_{HH} = 0,1)→H_{2}O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H_{2} is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 10^{4}.

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

Pages (from-to) | 3516-3522 |

Number of pages | 7 |

Journal | The Journal of chemical physics |

Volume | 77 |

Issue number | 7 |

DOIs | |

State | Published - 1982 |

## Fingerprint

Dive into the research topics of 'Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(n_{OH}) +H

_{2}(n

_{HH})→H

_{2}O+H'. Together they form a unique fingerprint.