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State‐resolved rotational energy transfer in open shell collisions: Cl( 2 P 3/2 )+HCl

State‐resolved rotational energy transfer in open shell collisions: Cl( 2 P 3/2 )+HCl Time‐ and frequency‐resolved infrared (IR) laser absorption methods are used to probe hot atom energy transfer in open shell interactions of Cl( 2 P 3/2 )+HCl( J ) in the single collision regime. The Cl( 2 P 3/2 ) atoms are prepared by 308 nm laser photolysis of Cl 2 , and suffer collisions at E rel ∼3500 cm −1 with a room temperature HCl distribution in a fast flow cell. Selective collisional excitation of final HCl( J f ) states is monitored by transient IR absorption on R ( J ≥4) branch lines in the HCl( v =1←0) band, while depletion of the initial HCl( J i ) states is monitored by transient bleaching of the room temperature Doppler profiles. Analysis of the J dependent Doppler profiles permits extraction of rotational loss σ loss ( J i )=∑ fP ( J i )⋅σ f ← i and gain σ gain ( J f )=∑ iP ( J i )⋅σ f ← i cross sections, as a function of initial and final J states, respectively. Absolute transient concentrations of the HCl( J i ) and HCl( J f ) are measured directly from absorbances via Beer’s Law, and used to extract absolute collisional cross sections. The results are compared with quasiclassical trajectory (QCT) calculations on a hybrid ab initio /LEPS surface of Schatz and Gordon, which prove remarkably successful in reproducing both the J dependent trends and absolute values of the state‐resolved gain and loss collision cross sections. © 1995 American Institute of Physics. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png The Journal of Chemical Physics American Institute of Physics
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