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Effect of orbital alignment on the forward and reverse electronic energy transfer Ca(4s5p /sup 1/P/sub 1/)+Marrow-right-leftCa(4s5p /sup 3/P/sub J/)+M with rare gases

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:6015929

Effects of orbital alignment on the relative cross sections for electronic energy transfer are determined for the near resonant transfer between Ca(4s5p /sup 1/P/sub 1/) and Ca(4s5p /sup 3/P/sub J/) states with rare gas collision partners. The experiments are carried out by pulsed laser excitation in a crossed beam. The results for the forward direction, /sup 1/P to /sup 3/P, formulated in terms of the ratio of the maximum to minimum transfer probability are: /sup 3/He 1.61 +- 0.05; He 1.60 +- 0.03; Ne 1.55 +- 0.10; Ar 1.52 +- 0.21; for Kr, transfer occurs, but no preference is distinguishable within 1 +- 0.2; Xe 1.44 +- 0.06. The results for He, Ne, and Ar indicate a clear preference in the transfer for the initially prepared molecular Pi state. For Xe the molecular ..sigma.. state is dominant. The energy transfer is also carried out in the reverse direction, /sup 3/P/sub 1/ to /sup 1/P, for He and Xe, obtaining 1.65 +- 0.10 and 1.94 +- 0.22, respectively. Analysis of the state preparation suggests that the reverse direction favors the asymptotic molecular ..sigma.. state for He and the molecular Pi state for Xe. These alignment results provide a first experimental determination of the dominant electronic states involved in a collisional energy transfer process.

Research Organization:
Joint Institute for Laboratory Astrophysics, National Bureau of Standards and University of Colorado; Departments of Physics and Chemistry, University of Colorado, Boulder, Colorado 80309-0440
OSTI ID:
6015929
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 87:7; ISSN JCPSA
Country of Publication:
United States
Language:
English