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On the orientation of molecular photofragments produced in highly excited rotational states

AuthorsBeswick J. Alberto; Glass-Maujean, M.; Roncero, Octavio
Issue Date1992
PublisherAmerican Institute of Physics
CitationJournal of Chemical Physics 96: 7514- 7527 (1992)
AbstractThe degree of orientation of highly excited rotational states of molecular fragments produced by photodissociation with circularly polarized light is studied quantum mechanically. It is shown that a significant orientation of the fragments' angular momentum j can be obtained when two or more dissociative continua correlated to the same final state of the products are excited simultaneously. In addition, the coherently excited continua should correspond to different helicity states, that is, to different projections of j on the reaction coordinate R (the vector joining the centers of mass of the fragments). The particular cases of an initial total angular momentum equal to zero as well as the axial recoil limit are discussed. The theory is applied to a simplified model of the photodissociation of ICN in the A continuum. The calculations have been performed by integration of the time independent quantum close-coupling equations for the coupling between the rotation of CN and the reaction coordinate R, using recently proposed potential energy surfaces and couplings. The results reproduce qualitatively the experimental results of Hasselbrink, Waldeck, and Zare [Chem. Phys. 126, 191 ( 1988)], in particular, the change of sign and the large degree of orientation found for highly excited rotational states of the CN fragments. © 1992 American Institute of Physics.
Identifiersdoi: 10.1063/1.462403
issn: 0021-9606
Appears in Collections:(CFMAC-IFF) Artículos
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