A comparison of the two-state approximation and multistate treatments for vibration–vibration energy exchange in molecular collisions

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Abstract
We have solved the time‐dependent Schrödinger equation based on a semiclassical collision to examine deviations of the two‐state approximation from multistate treatments for vibration–vibration energy exchange processes. For a specific case of 41→50 in D2+D2, the two‐state calculation of energy exchange probabilities fails at high collision energies (E≳2h/ω, where ω is the frequency of the oscillator). A thermal average shows that the approximation leads to large deviatons above 2000 °K.