unified impact theory for velocity-changing effects and speed dependencies in neutral species lineshapes统一理论影响velocity-changing效果和速度依赖性lineshapes中立的物种.pdfVIP

Hindawi Publishing Corporation International Journal of Spectroscopy Volume 2010, Article ID 306392, 9 pages doi:10.1155/2010/306392 Research Article Unified Impact Theory for Velocity-Changing Effects and Speed Dependencies in Neutral Species Lineshapes Roger M. Herman Department of Physics, The Pennsylvania State University, 104 Davey Laboratory, University Park, PA 16802, USA Correspondence should be addressed to Roger M. Herman, rmh@ Received 27 April 2009; Accepted 19 July 2009 Academic Editor: Roland Stamm Copyright © 2010 Roger M. Herman. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. A dipole correlation function which incorporates velocity-changing (motional narrowing) effects and the effects of speed- dependent Lorentz relaxation rates into otherwise Voigt profile correlation functions is developed, based partly upon previous work by the author. For the first time simple closed expressions, which lend themselves to elementary calculation beginning only with the relevant parts of intermolecular interaction energies, are developed for the cubic time-dependent term within the exponent describing the decay of the correlation function. This term is of first order in perturber number density, as are the Lorentz parameters, and is complex, thereby allowing for narrowing, changing in shape and asymmetry in the line profile. “Soft” and “hard” collisions play no explicit role, though both are variously present for each line. Quartic time dependencies are also discussed, though they are thought to be negligible in nonhydrogen molecular spectroscopy. Finally, some comments are added about a relevant t