Chaos and incoherence in a classical rotation-vibration model of infrared multiple-photon excitation

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Abstract
By including rotations in a previously developed generic vibrational model of ir multiple-photon excitation (MPE) [Phys. Rev. Lett. 51, 1259 (1983) and Phys. Rev. A 34, 1211 (1986)] it is found that the combination of chaotic dynamics and rotational averaging leads to fluence-dependent absorption and removes the sensitivity of the results to model-dependent parameters. Therefore, a complete propagation calculation through a molecular medium of this type would show a Beer’s law absorption of photons consistent with the vast majority of MPE experiments performed to date, a result which previously was attributed to rate-equation dynamics in the molecular quasicontinuum. In addition, the classical rotation-vibration dynamics observed in this model correlate very well with one’s quantum intuition based on a molecule’s P-, Q-, and R-branch structure and on the red shift of the vibrational absorption feature with excitation.

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