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Phys Chem Chem Phys. 2011 May 21;13(19):8857-68. doi: 10.1039/c0cp01882a. Epub 2011 Apr 4.

Doublet rotational energy transfer of the SH (X ²Π, v''=0) state by collisions with Ar.

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  • 1Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.

Abstract

The rotational energy transfer (RET) by Ar collisions within the SH X (2)Π (v'' = 0, J'' = 0.5-10.5) state is characterized. The integral cross sections as a function of collision energy for each rotational transition are calculated using a quantum scattering method in which the constructed potential energy functions are based on a ground state potential energy surface (PES) reported previously. On the other hand, a laser-induced excitation fluorescence technique is employed to monitor the relaxation of the rotational population as a function of photolysis-probe delay time following the photodissociation of H(2)S at 248 nm. The rotational population evolution is comparable to its theoretical counterpart based on calculated Λ-resolved RET rate constants. The propensity in Λ-resolved RET transitions is found to approximately resemble the case of OH(X (2)Π, v'' = 0) + Ar. The Λ-averaged RET collisions are also analyzed and result in several propensity rules in the transitions. Most propensity rules are similar to those observed in the collisions of SH(A (2)Σ(+)) by Ar. However, the behavior of the conserving ratio, defined as rate constants for spin-orbit conserving transition divided by those for spin-orbit changing transition, shows distinct difference from those described by Hund's case (b).

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