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arXiv:2610.11686

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

Sameernandan Upadhyayula, Jiří J. L. Vaníček

physics.chem-phquant-phSubmitted Oct 8, 2026• Announced Oct 9, 2026• 0 citations
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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.

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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.
This paper presents a nonperturbative treatment of strong-coupling induced effects in atom-field systems which cannot be seen in traditional perturbative treatments invoking compromising assumptions such as the Born-Markov, rotating wave, or Fermi Golden rule. We consider an atom whose internal degrees of freedom are modeled by a harmonic oscillator which is bilinearly coupled to a scalar quantum field, representing one of the two polarizations of an electromagnetic field. Because the whole system is Gaussian we can solve this problem exactly. Using the open quantum system conceptual framework and the influence functional formalism we derive the dynamics of the reduced density matrix for the atom which enables the calculation of atomic transition probability and other relevant physical quantities. Finding an exact solution to this problem has the distinct advantage of enabling one to capture fully the strong coupling regime and discover interesting effects such as spontaneous ground state excitation [R. Passante, T. Petrosky, and I. Prigogine, Long-time behaviour of self-dressing and indirect spectroscopy, Physica (Amsterdam) 218A, 437 (1995).] which is unfathomable in perturbative treatments. The conventional description of atomic-optical activities is predicated on the assumption that the state of the total atom-field system is a product state of the atomic excitations and the photon number states, an assumption which is valid only for vanishingly weak coupling. The correct energy eigenfunctions to use should be that of the Hamiltonian of the combined atom-field system. Other features associated with finite to strong coupling effects such as resonance peak broadening and transition from a gapped to a gapless spectrum can all be understood from this perspective. Finally, to put the issues in a proper perspective we take the perturbative limit of the exact results and compare them with those from conventional time-dependent perturbation theory (TDPT). This enables one to pin-point where the deficiencies of TDPT lie as one removes the ultraweak coupling assumption.
Abstract The mechanism of ultrafast, coherent Raman transitions driven at high field strengths is explored in theory and experiment. The study addresses the possibility of maintaining control of a vibrational wavepacket that is guided to a desired final state during the course of a Raman excitation by significantly perturbing the participating molecular states on the time scale of the dynamics under manipulation. Variations in the sequence and amplitude of the pulsed laser fields give direct insight into the nature of the perturbation as well as the population flow within vibrational manifolds of the electronic states involved in the transition. The excitation scheme realized in this work demonstrates control over the dynamics of a molecular system through a non‐adiabatic pathway that utilizes the full manifold of dressed states induced by the laser fields driving the transition rather than isolating the system in a decoupled dressed state common for the adiabatic passage scheme. By preparing highly excited virbrational states in molecular iodine with this scheme, it is shown that a vibrational wavepacket can be steered by controlling the phase with which the character of the field‐free states is introduced into the manifold of dressed states participating in the transition. This scheme seeks to open the possibility of using ultrafast Raman excitation for initiating and observing chemical reactions in the electronic ground state of a molecular system. Copyright © 2007 John Wiley & Sons, Ltd.
We present a novel approach to molecular spectroscopy with light pulses of arbitrary strength and duration. The key quantity is the frequency-resolved net energy transfer dE/dω which reveals at which frequencies energy is transferred from the field to the molecule (absorption) or from the molecule to the field (stimulated emission). It is shown that dE/dω can be expressed as the Fourier transform of the cross-correlation function of the molecular polarization P(t) and the time derivative of the applied field, dℰ/dt. In this sense, it is formally equivalent to the absorption cross section under weak-field conditions which, as commonly known, can be represented as the Fourier transform of the autocorrelation function S(t). The time-dependent polarization P(t) is determined by exact integration of the time-dependent Schrödinger equation including the light-matter interaction to all orders. It is shown that under weak-field conditions the expression for dE/dω reduces to the well-known cross section formula in the time-dependent picture of spectroscopy, multiplied by the spectral intensity of the light pulse. Therefore, we consider the expression for the frequency-resolved energy transfer, which is valid for arbitrary electric fields, as the natural extension of the absorption cross section in the weak-field limit. Furthermore, dE/dω is shown to be formally equivalent to the change of the spectral intensity, ΔI(ω), of an optical pulse after transmission through a sample, the latter being derived by solving Maxwell’s equations under well-known approximations. The theory is applied to a simple one-dimensional model with two electronic states and the frequency-resolved energy transfer is investigated as a function of the field strength. For sufficiently strong fields, dE/dω exhibits transitions between essentially all vibrational levels in the ground and all states in the excited electronic manifold. The new expression distinguishes between absorption and emission and that is clearly seen in the spectra.
A nonperturbative treatment of the dynamical behavior of a vibronic system in a resonant, coherent, driving light field is developed. The potential energy surfaces for the vibrational motion in the electronic ground and excited state are assumed to be displaced and distorted relative to one another. A system of three integrodifferential equations is derived from the infinite set of density-matrix equations. Both approximate analytical and numerical solutions are presented for the intensity and the intensity-correlation function of the scattered light. The results are valid for arbitrary ratios of the Rabi frequency to the relaxation rates. A system with fast vibrational relaxation behaves as a two-level system. For systems with slow vibrational relaxation, the applicability of perturbation theory requires pump fields that are weaker than those of a two-level system. The Rabi oscillations occurring in a strong pump field are damped less than those of a two-level system, and the intensity substantially decreases. The long-time behavior (determined by the vibrational relaxation time) is characterized by the increase of the intensity toward its stationary value.
Laser-controlled ultrafast state-selective vibrational dynamics of diatomic molecules, which are coupled to an unobserved quasiresonant environment is investigated using the reduced density-matrix formalism beyond and within a Markov-type approximation. Dissipative quantum dynamics in a classical electric field of shaped infrared ultrashort laser pulses is simulated for a one-dimensional nondissociative Morse oscillator, representing the local OH bond in the H2{\mathrm{H}}_{2}H2​ O and HOD molecules in the electronic ground state. Localization of population at a prescribed vibrational target level of OH up to v=10 with probability of about 90% is demonstrated on a picosecond time scale, while the strength of the quasiresonant molecule-environment coupling results in subpicosecond lifetimes of the vibrational states. The laser-controlled stabilization of selective excitation in the restricted set of vibrational states against a background of strongly diminished relaxation to lower vibrational states is also shown. The laser-control scheme may include a superposition of several laser pulses. A Markov-type approximation results in slightly increased lifetimes of the vibrational states, along with decreased predicted probability of state-selective excitation of a molecule by about 20--30%. Several results obtained within the fourth-order perturbation theory in interaction of a molecule with an environment are in a good agreement with the non-Markov analysis.
The nonequilibrium dynamics of molecular devices is studied in the framework of a generic model for single-molecule transistors: a resonant level coupled by displacement to a single vibrational mode. In the limit of a broad level and in the vicinity of the resonance, the model can be controllably reduced to a form quadratic in bosonic operators, which in turn is exactly solvable. The response of the system to a broad class of sudden quenches and ac drives is thus computed in a nonperturbative manner, providing an asymptotically exact solution in the limit of weak electron-phonon coupling. From the analytic solution, we are able to (1) explicitly show that the system thermalizes following a local quantum quench, (2) analyze in detail the time scales involved, (3) show that the relaxation time in response to a quantum quench depends on the observable in question, and (4) reveal how the amplitude of long-time oscillations evolves as the frequency of an ac drive is tuned across the resonance frequency. Explicit analytical expressions are given for all physical quantities and all nonequilibrium scenarios under study.