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ABSTRACT

Green and Zare 1975

Green, S., and R.N. Zare, 1975: Mechanism for collision-induced transitions between Λ-doublets in 1Π molecules: Reduction to a single scattering potential. Chem. Phys., 7, 62-72, doi:10.1016/0301-0104(75)85025-7.

The theory is presented for rotational excitation of 1Π molecules by collisions with rare gas atoms. It is shown that collision dynamics are described by the two electronic potential energy surfaces which correlate with the electronically degenerate Λ components (doublets) in the diatomic molecule. Because the °Λ degeneracy can alternatively be described as being in the rotational rather than in the electronic degree of freedom, one can reformulate the collision dynamics in terms of a single effective electronic potential which then depends on Φ, the angle of rotation about the diatomic axis. The form of this Φ dependence is found to be identical to that postulated to explain experimental data for collisional transfer of laser-induced fluorescence.

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