Electronic Coherences in Molecules: The Projected Nuclear Quantum Momentum as a Hidden Agent

2024/05/01 by Evaristo Villaseco Arribas, Neepa T. Maitra, Arribas, Evaristo Villaseco +1 · 3 citations
Chemistry · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Molecular Spectroscopy and Structure #Molecular spectroscopy and chirality #Spectroscopy and Quantum Chemical Studies

paper · pdf · doi:10.48550/arxiv.2405.00649

openalex publication_date 2024/05/01 · openalex created_date 2024/05/05 · openalex updated_date 2026/07/31

Abstract

Electronic coherences are key to understanding and controlling photo-induced molecular transformations. We identify a crucial quantum-mechanical feature of electron-nuclear correlation, the projected nuclear quantum momenta, essential to capture the correct coherence behavior. In simulations, we show that, unlike traditional trajectory-based schemes, exact-factorization-based methods approximate these correlation terms, and correctly capture electronic coherences in a range of situations, including their spatial dependence, an important aspect that influences subsequent electron dynamics and that is becoming accessible in more experiments.

Cited by

• Exact-factorization framework for electron-nuclear dynamics in electromagnetic fields
• Unifying Decoherence and Phase Evolution in Mixed Quantum-Classical Dynamics through Exact Factorization
• Non-adiabatic perturbation theory of the exact factorisation

Related

• Electronic decoherence along a single nuclear trajectory
• Long-Lived Electronic Coherences from First Principles
• Unifying Decoherence and Phase Evolution in Mixed Quantum-Classical Dynamics through Exact Factorization
• Decoherence in Molecular Electron Spin Qubits: Insights from Quantum Many-Body Simulations
• Analysis of divergent dynamics of exactly factorized electron-nuclear wavefunctions