An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chemistry computation is required at each time step since there is only a single time-dependent potential surface. Also shown is the close relationship to the "exact factorization method." The quantum Ehrenfest method is compared with vMCG for study of electron dynamics in a modified bismethylene-adamantane cation system. Illustrative examples of electron-nuclear dynamics are presented for a distorted allene system and for HCCI where one has a degenerate Π system.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1063/1.5038428 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Influence of nonequilibrium vibrational dynamics on spin selectivity in chiral molecular junctions.
J Chem Phys
January 2025
Institute of Physics, University of Freiburg, Hermann-Herder-Strasse 3, 79104 Freiburg, Germany.
We explore the role of molecular vibrations in the chirality-induced spin selectivity (CISS) effect in the context of charge transport through a molecular nanojunction. We employ a mixed quantum-classical approach that combines Ehrenfest dynamics for molecular vibrations with the hierarchical equations of motion method for the electronic degrees of freedom. This approach treats the molecular vibrations in a nonequilibrium manner, which is crucial for the dynamics of molecular nanojunctions.
View Article and Find Full Text PDFQuantum Electrodynamics in High-Harmonic Generation: Multitrajectory Ehrenfest and Exact Quantum Analysis.
J Chem Theory Comput
December 2024
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 PDFShort-time accuracy and intra-electron correlation for nonadiabatic quantum-classical mapping approaches.
J 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 PDFReal-Time CASSCF (Ehrenfest) Modeling of Electron Dynamics in Organic Semiconductors. Dynamics Reaction Paths Driven by Quantum Coherences. Application to a Radical Organic Semiconductor.
J Phys Chem A
December 2024
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, White City Campus 80 Wood Lane, W12 0BZ London, United Kingdom.
We present a strategy for the modeling of charge carrier dynamics in organic semiconductors using conventional quantum chemistry methods, including the analytic gradient for nuclear motion. The theoretical approach uses real-time CASSCF (Ehrenfest) all-electron dynamics coupled to classical nuclear dynamics for the special case of a small number (4-8) of molecular units. The objective is to obtain mechanistic/atomistic insight at the electronic structure level, relating to spin density dynamics, to the effect of crystal structure (e.
View Article and Find Full Text PDFToward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations.
J Phys Chem Lett
November 2024
Hamburg Center for Ultrafast Imaging, Universität Hamburg and Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany.
The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat electronic coherence. However, the most popular and practical nonadiabatic molecular dynamics techniques, Tully's fewest-switches surface hopping and Ehrenfest mean-field dynamics, are unable to describe the dynamics proceeding from an initial electronic coherence. While such issues are not encountered with the analogous coupled-trajectory algorithms or numerically exact quantum dynamics methods, applying such techniques necessarily comes with a higher computational cost.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!