## Abstract

A new method is suggested for the calculation of the microcanonical cumulative reaction probability via flux autocorrelation relations. The Hamiltonian and the flux operators are computed in a discrete variable representation (DVR) and a well-behaved representation for the Green's operator, G(E^{+}), is obtained by imposing absorbing boundary conditions (ABC). Applications to a one-dimensional-model problem and to the collinear H + H _{2} reaction show that the DVR-ABC scheme provides a very efficient method for the direct calculation of the microcanonical probability, circumventing the need to compute the state-to-state dynamics. Our results indicate that the cumulative reaction probability can be calculated to a high accuracy using a rather small number of DVR points, confined to the vicinity of the transition state. Only limited information regarding the potential-energy surface is therefore required, suggesting that this method would be applicable also to higher dimensionality problems, for which the complete potential surface is often unknown.

Original language | English (US) |
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Pages (from-to) | 4412-4422 |

Number of pages | 11 |

Journal | The Journal of Chemical Physics |

Volume | 96 |

Issue number | 6 |

DOIs | |

State | Published - 1992 |

## ASJC Scopus subject areas

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry