On-the-fly ab initio semiclassical evaluation of electronic coherences in polyatomic molecules reveals a simple mechanism of decoherence

Abstract

Irradiation of a molecular system by an intense laser field can trigger dynamics of both electronic and nuclear subsystems. The lighter electrons usually move on much faster, attosecond time scale but the slow nuclear rearrangement damps ultrafast electronic oscillations, leading to the decoherence of the electronic dynamics within a few femtoseconds. We show that a simple, single-trajectory semiclassical scheme can evaluate the electronic coherence time in polyatomic molecules accurately by demonstrating an excellent agreement with full-dimensional quantum calculations. In contrast to numerical quantum methods, the semiclassical one reveals the physical mechanism of decoherence beyond the general blame on nuclear motion. In the propiolic acid, the rate of decoherence and the large deviation from the static frequency of electronic oscillations are quantitatively described with just two semiclassical parameters---the phase space distance and signed area between the trajectories moving on two electronic surfaces. Because it evaluates the electronic structure on the fly, the semiclassical technique avoids the "curse of dimensionality" and should be useful for preselecting molecules for experimental studies.

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Cited by in corpus (16)

• Decoherence and Revival in Attosecond Charge Migration Driven by Non-adiabatic Dynamics
• Core-valence attosecond transient absorption spectroscopy of polyatomic molecules
• On-the-fly ab initio semiclassical evaluation of third-order response functions for two-dimensional electronic spectroscopy
• Mapping Electronic Decoherence Pathways in Molecules
• Search for long lasting electronic coherence using on-the-fly ab initio semiclassical dynamics
• Representing Molecular Ground and Excited Vibrational Eigenstates with Nuclear Densities obtained from Semiclassical Initial Value Representation Molecular Dynamics
• The role of symmetric vibrational modes in the dehoherence of correlation-driven charge migration
• Probing Vibronic Coherence in Charge Migration of Molecules Using Strong Field Sequential Double Ionization
• High-order geometric integrators for the local cubic variational Gaussian wavepacket dynamics
• Isotope effects in the electronic spectra of ammonia from ab initio semiclassical dynamics
• On Hagedorn wavepackets associated with different Gaussians
• How to find molecules with long-lasting charge migration?
• Can increasing the size and flexibility of a molecule reduce decoherence and prolong charge migration?
• Control of valence-electron motion in Xe cations using the stimulated-Raman-adiabatic-passage technique
• Applicability of the thawed Gaussian wavepacket dynamics to the calculation of vibronic spectra of molecules with double-well potential energy surfaces
• Efficient Semiclassical Evaluation of Electronic Coherences in Polyatomic Molecules