## Abstract

The polarization of Cl(P-2(3/2)) atoms resulting from photodissociation of ICl in the range 490nm to 560nm has been analysed in detail. The most accurate-to-date set of the five Omega = 0(+) and Omega = 1 adiabatic potential energy surfaces that correlate to the ground state Cl(P-2(3/2)) + I(P-2(3/2)) atoms have been constructed from available spectroscopic, ab initio, and long-range perturbation-theory data. Simulations of the photolysis-energy dependence of Cl-atom polarization, show non-adiabatic transitions occurring at R-x similar to 6.5 angstrom, with probabilities from B((3)Pi(0+)) to X((1)Pi(0+)) (P = 0.96), A((3)Pi(1)) to a((3)Pi(1)) (P = 0.12), and A((3)Pi(1)) to z((1)Pi(1)) (P = 0.49). The simulations are shown to be sensitive to changes in the potential energy surfaces on the order of Delta V = 30 cm(-1) angstrom, reinforcing that these type of polarization experiments serve as an exceedingly stringent test of theory.

Original language | English |
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Pages (from-to) | 1665-1676 |

Number of pages | 12 |

Journal | Molecular Physics |

Volume | 103 |

Issue number | 13 |

DOIs | |

Publication status | Published - 10 Jul 2005 |