Sensitivity analysis of rotational energy transfer processes to the intermolecular potential

Larry Eno, Herschel Rabitz

Research output: Contribution to journalArticle

21 Scopus citations

Abstract

This paper considers the sensitivity of rotational energy transfer processes to the variation of parameters within an assumed model intermolecular potential. The following cross sections are considered here: integral state to state, pressure broadening, effective diffusion and viscosity, and final state summed integral cross sections. In order to simplify the calculation of cross sections, attention is restricted to the scattering of an atom and linear rigid rotor. Furthermore, the collision dynamics are approximated by using the infinite order sudden (IOS) method. It is shown that use of the IOS method allows for the very simple generation of first order sensitivity coefficients (i.e., the partial derivative of cross sections with respect to potential parameters). Particular attention is focused upon the sensitivities of different cross sections and combinations of cross sections to the various parameters. The first order sensitivities are also used to derive new coefficients which describe how the potential parameters correlate given a limited set of cross section measurements. These coefficients are shown to be particularly important in determining the degree to which a set of measurements is able to define various parameters of the assumed potential.

Original languageEnglish (US)
Pages (from-to)2314-2323
Number of pages10
JournalThe Journal of chemical physics
Volume72
Issue number4
DOIs
StatePublished - Jan 1 1980

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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