### Abstract

The photodissociation reaction of ICN in the A continuum has been theoretically studied based on ab initio potential energy surfaces and classical trajectories. Ab initio contracted spin-orbit configuration interaction calculations have been carried out to obtain potential energy surfaces (PES's) of ^{3}Π_{1}, ^{3}Π_{0+} and ^{1}Π_{1} excited states, where results are fit to five diabatic potential functions and their couplings as functions of all three internal degrees of freedom. The transition dipoles at the Franck-Condon region have also been calculated. All the PES's involved in photodissociation are bent near the Franck-Condon region. Classical trajectory calculations performed on these potential surfaces have produced results that are in agreement with various experimental findings and provide a basis for their interpretation. The calculations indicate that the absorption is a mixture of parallel and perpendicular transition. A reasonable I/I* branching ratio can be obtained by considering the effect of initial bending vibrations in addition to the character of mixed transitions. The I/I* channel selectivity of the CN rotation can be compared to the shape of PES's with respect to the bending angle. The rotational excitation of the CN fragment is determined by the shape of PES's on which trajectories travel before and after the transition. The higher rotational component in the I channel is attributed to the energy gradient of ^{1}Π_{1} with respect to the bending angle at the transition region where the C-I distance is between 5.0 and 8.0 a.u. The lower component in the I channel emerges from ^{3}Π_{1}. The average rotational distribution obtained with the proper weight of Boltzmann populations and transition intensities is in agreement with the experiment. This interpretation can also be applied to the rotational quantum number dependence of anisotropy parameters. Trajectory calculations on the ^{3}Π _{1} surface alone, give a single Boltzmann rotational distribution. Reflecting the shape of PES's with respect to the CN distance, the product CN vibration on ^{3}Π_{0+} and ^{1}Π becomes suppressed while that on ^{3}Π_{1} becomes slightly more excited. The anisotropic parameter was also analyzed. Some comments on the femtosecond transition spectroscopy are also made.

Original language | English |
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Pages (from-to) | 4894-4909 |

Number of pages | 16 |

Journal | The Journal of Chemical Physics |

Volume | 100 |

Issue number | 7 |

DOIs | |

Publication status | Published - 1994 Jan 1 |

Externally published | Yes |

### ASJC Scopus subject areas

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

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## Cite this

*The Journal of Chemical Physics*,

*100*(7), 4894-4909. https://doi.org/10.1063/1.467209