Collision matrix elements near a pseudocrossing of potential energy curves

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The behavior of the matrix element of the collision operator, d/dR, between adiabatic states with variations in R, the internuclear separation, is studied qualitatively for diatomic molecules. These matrix elements often have a maximum or a zero near the pseudocrossing of the two adiabatic potential energy curves. Effects of these extremes of behavior on cross sections are considered and limits on the validity of approximations which use R-independent orbitals are developed. Finally, the effect of a second pseudocrossing on these matrix elements is analyzed.

Original languageEnglish (US)
Pages (from-to)3899-3904
Number of pages6
JournalThe Journal of chemical physics
Issue number9
StatePublished - 1972
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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