Vector properties of S(P-3) and S(D-1) in the photodissociation of SH: Quantum interference and overlapping resonance

Abstract

A quantal analysis is presented for the vector properties of the S(P-3) and S(D-1) fragments produced in the photodissociation of SH. We find that several different kinds of effects influence the angular distributions and the alignments of the sulfur atoms. At energies between the thresholds to the S(P-3) and S(D-1) terms, the vector properties are constant near the isolated Lorentzian resonances. The vector properties for the overlapping resonances, show rapid changes due to the difference of the geometrical factors characterizing the individual resonance. For the highest levels (v(')=6,N(')greater than or equal to6), quantum interference between the predissociative (via the bound A (2)Sigma(+) state) and the direct (by the repulsive (2)Sigma(-) state) pathways produces strong variations in the values of vector properties across the asymmetric resonances, suggesting a convenient means of angular control of the different atomic terms or the fine structure components of a given atomic term. At energies above the threshold to the S(D-1) term, the interference between the two direct dissociating routes [through the A (2)Sigma(+) and (2)Sigma(-) states for the S(P-3) product, and through the (2)Delta and 2(2)Pi states for the S(D-1) product] is shown to yield highly oscillatory variations of the vector properties. (C) 2002 American Institute of Physics.