Non-Perturbative Vibrational Excitation by Arbitrary Electric Fields from Classical Phase-Space Dynamics

Abstract

We present a non-perturbative framework for the quantum treatment of vibrational excitation in molecular systems driven by electric fields with arbitrary time dependence. For harmonic potentials with linear dipole coupling, the field-induced dynamics is exactly described by a displaced coherent state, whose evolution is completely determined by a complex phase-space coordinate. Closed-form expressions for this coordinate reveal a clear distinction between resonant and non-resonant regimes. The resulting vibrational populations follow a Poisson distribution determined by a dimensionless time-dependent phase-space displacement, for both resonant and non-resonant driving. Resonant driving results in an enhanced phase-space displacement, whereas finite detuning between the driving and vibrational frequencies leads to an exponential suppression of the phase-space displacement and vibrational excitation. While the approach reduces to the standard time-dependent perturbation theory in the weak-field limit, it remains valid in the strong-field regime, where perturbative treatments fail. Our results provide a transparent phase-space picture of vibrational control and enable non-perturbative state preparation in ultrafast spectroscopy.