We consider an Ehrenfest approximation for a particle in a double-well potential in the presence of an external environment schematized as a finite resource heat bath. This allows us to explore how the limitations in the applicability of Ehrenfest dynamics to nonlinear systems are modified in an open system setting. Within this framework, we have identified an environment-induced spontaneous symmetry breaking mechanism, and we argue that the Ehrenfest approximation becomes increasingly valid in the limit of strong coupling to the external reservoir, either in the form of an increasing number of oscillators or increasing temperature. The analysis also suggests a rather intuitive picture for the general phenomenon of quantum tunneling and its interplay with classical thermal activation processes, which may be of relevance in physical chemistry, ultracold atom physics, and fast-switching dynamics such as in superconducting digital electronics.
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http://dx.doi.org/10.1103/PhysRevE.92.042907 | DOI Listing |
J Chem Theory Comput
January 2025
Max Planck Institute for the Structure and Dynamics of Matter, Luruper Ch 149, Hamburg 22761, Germany.
High-harmonic generation (HHG) is a nonlinear process in which a material sample is irradiated by intense laser pulses, causing the emission of high harmonics of incident light. HHG has historically been explained by theories employing a classical electromagnetic field, successfully capturing its spectral and temporal characteristics. However, recent research indicates that quantum-optical effects naturally exist or can be artificially induced in HHG, such as entanglement between emitted harmonics.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Pitaevskii BEC Center, CNR-INO and Dipartimento di Fisica, Università di Trento, Via Sommarive 14, Trento I-38123, Italy.
Nonadiabatic quantum-classical mapping approaches have significantly gained in popularity over the past several decades because they have acceptable accuracy while remaining numerically tractable even for large system sizes. In the recent few years, several novel mapping approaches have been developed that display higher accuracy than the traditional Ehrenfest method, linearized semiclassical initial value representation (LSC-IVR), and Poisson bracket mapping equation (PBME) approaches. While various benchmarks have already demonstrated the advantages and limitations of those methods, unified theoretical justifications of their short-time accuracy are still demanded.
View Article and Find Full Text PDFJ Chem Phys
October 2024
Physical and Theoretical Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach to surface hopping. In contrast to standard fewest-switches surface hopping, this method propagates the classical degrees of freedom deterministically on the most populated adiabatic electronic state. This correctly preserves the equilibrium distribution of a quantum charge coupled to classical phonons, allowing one to time-average along trajectories to improve the statistical convergence of the calculation.
View Article and Find Full Text PDFJ Chem Phys
August 2024
CNRS, Institut de Chimie Physique UMR8000, Université Paris-Saclay, 91405 Orsay, France.
We employ the exact-factorization formalism to study the coupled dynamics of photons, electrons, and nuclei at the quantum mechanical level, proposing illustrative examples of model situations of nonadiabatic dynamics and spontaneous emission of electron-nuclear systems in the regime of strong light-matter coupling. We make a particular choice of factorization for such a multi-component system, where the full wavefunction is factored as a conditional electronic amplitude and a marginal photon-nuclear amplitude. Then, we apply the coupled-trajectory mixed quantum-classical (CTMQC) algorithm to perform trajectory-based simulations, by treating photonic and nuclear degrees of freedom on equal footing in terms of classical-like trajectories.
View Article and Find Full Text PDFJ Chem Phys
July 2024
Division of Arts and Sciences, NYU Shanghai, 567 West Yangsi Road, Shanghai 200124, China.
Accurate quantum dynamics simulations of nonadiabatic processes are important for studies of electron transfer, energy transfer, and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate nonadiabatic dynamics methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation of high-dimensional arrays, including TT-KSL for zero-temperature dynamics and TT-thermofield dynamics for finite-temperature dynamics. The approximate nonadiabatic dynamics methods investigated include mixed quantum-classical Ehrenfest mean-field and fewest-switches surface hopping, linearized semiclassical mapping dynamics, symmetrized quasiclassical dynamics, the spin-mapping method, and extended classical mapping models.
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