## Abstract

The time-dependent semiclassical equations are solved in analytical form for the case of a straight-line classical trajectory which passes near a point of accidental degeneracy of Σ^{+}, π and Σ^{-} states in a linear triatomic system. The configurational displacements from the point of intersection are assumed to be linear functions of time. The asymptotic analysis of the exact solution in the limits t → ±∞ yields the four-channel S-matrix, which gives all transition amplitudes (that is, transition probabilities and phases) of the problem. The model illustrates the importance of quantum interference effects in the case of a crossing of potential-energy surfaces of more than two electronic states. The results derived in this work may prove useful for trajectory-surface-hopping calculations in the case of a potential-surface crossing of Σ^{+}, π and Σ^{-} electronic states.

Original language | English |
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Pages (from-to) | 215-228 |

Number of pages | 14 |

Journal | Chemical Physics |

Volume | 279 |

Issue number | 2-3 |

DOIs | |

State | Published - 1 Jun 2002 |

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