Abstract
When two atoms are in proximity, their resonance lines are broadened because of the formation of molecular potentials, between which photon transitions can occur. The level of experimental refinement in measuring excimer and collisional far-wing spectra calls for interpretive theoretical methods that accurately treat the observed structure in line shapes. Of particular interest are satellites and undulations, for they can give much information on intermolecular potentials. We derive an expression for T-matrix elements, based on JWKB wave functions and stationary-phase techniques, that is universally applicable to situations with one, two, or more Condon points. Each transition point is treated individually, with effects of potential shape, wave-function phases, and interference separately highlighted. The expression is tested against quantum-mechanical line shapes of the red and blue wings of the Rb D lines broadened by Xe perturbers. Agreement is quite good for both the red-wing undulations and the blue-wing satellite-supernumerary structure. © 1983 The American Physical Society.
Recommended Citation
R. J. Bieniek and T. J. Streeter, "Universal Stationary-phase Treatment Of Far-wing And Excimer Spectral Line Shapes," Physical Review A, vol. 28, no. 6, pp. 3328 - 3333, American Physical Society, Jan 1983.
The definitive version is available at https://doi.org/10.1103/PhysRevA.28.3328
Department(s)
Physics
International Standard Serial Number (ISSN)
1050-2947
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2023 American Physical Society, All rights reserved.
Publication Date
01 Jan 1983
