Vibrational energy transfer from highly excited anharmonic oscillators. Dependence on quantum state and interaction potential

In order to elucidate the general features of vibrational deactivation of highly excited anharmonic oscillators, we present quasiclassical trajectory calculations on prototype collinear I2 (v)‐inert gas collision systems. The results for vibrational‐translational energy transfer reveal several interesting trends as a function of initial vibrational quantum state, projectile mass, and projectile–oscillator interaction potential. (1) Vibrational deactivation is inefficient from all quantum levels and for all projectile masses. The average energy transfer per collision ΔE is strongly peaked at intermediate vibrational levels (v≊80) and is observed to be at most ≊−kbT. Furthermore, when scaled to h/ω(E), the ’’local’’ oscillator energy spacing, ΔE can be accurately represented by a simple power law in vibrational quantum number over a wide range of bound states. (2) Energy transfer is progressively less efficient from levels in the neighborhood of and approaching dissociation. (3) Vibrational energy loss for ...

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