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Updated: Dec 4, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
Published on: August 6, 2018
Time-independent quantum theory on vibrational inelastic scattering between atoms and open-shell diatomic molecules:
1Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Abstract:
A full-dimensional rigorous quantum mechanical treatment of non-reactive inelastic scattering of an open-shell diatom [e.g., NO(2Π)] with a structureless and spinless atom is presented within the time-independent close-coupling framework. The inclusion of the diatomic vibrational degree of freedom allows the investigation of transitions between different vibrational manifolds, in addition to those between different rotational, spin-orbit, and Λ-doublet states. This method is applied to the scattering of vibrationally excited NO(2Π) with Ar and H (with its spin ignored). The former has negligible vibrational inelasticity, thanks to the weak interaction between the two collisional partners. This conclusion justifies the commonly used two-dimensional approximation in treating NO scattering with rare gas atoms. The latter, on the other hand, is shown to undergo significant vibrational relaxation, even in the ultra-cold regime, owing to a chemically bonded (HNO) complex on the lowest-lying singlet potential energy surfaces.
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