Relationship between bipolar moments and molecule-frame polarization parameters in Doppler photofragment spectroscopy
Journal Article
·
· Journal of Chemical Physics
- Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, 711 10 Heraklion-Crete (Greece)
- Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)
- Department of Chemistry, Stanford University, Stanford, California 94305-5080 (United States)
In terms of the molecular-frame polarization parameters {bold a}{sub {bold q}}{sup ({bold k})}(p), an equation is derived that describes the shape of a photofragment Doppler profile as a function of the three angles {Gamma}, {Delta}, and {Phi} that specify the photolysis and probe laser polarizations about the detection axis. This expression is specialized to linearly polarized photolysis and probe laser beams. For the particular value of the angle between the probe laser polarization and the detection axis, {Delta}={pi}/2, this equation can be reduced to the form of well-known laboratory-frame expressions that use the bipolar moment formalism introduced by Dixon. Comparison of these forms shows the equivalence of the two formalisms and gives the relationships between the bipolar moments {beta}{sub Q}{sup K}(k{sub 1}k{sub 2}) and the molecule-frame {bold a}{sub {bold q}}{sup ({bold k})}(p) parameters. We show that linear combinations of the bipolar moments completely describe photofragment polarization in the molecular frame and possess distinct quantum mechanical significance. In particular, it is shown that the coherent contribution to the photofragment alignment is proportional to the linear combination (1/5){beta}{sub 0}{sup 2}(02){minus}(1/7){beta}{sub 0}{sup 2}(22){minus}(12/35){beta}{sub 0}{sup 2}(42). {copyright} {ital 1999 American Institute of Physics.} thinsp
- OSTI ID:
- 687994
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 111; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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