skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Understanding the nature of mean-field semiclassical light-matter dynamics: An investigation of energy transfer, electron-electron correlations, external driving, and long-time detailed balance

Abstract

Semiclassical electrodynamics (with quantum matter plus classical electrodynamics fields) is an appealing approach for studying light-matter interactions, especially for realistic molecular systems. However, there is no unique semiclassical scheme. On the one hand, intermolecular interactions can be described instantaneously by static two-body interactions connecting two different molecules, while a classical transverse E field acts as a spectator at short distance; we will call this Hamiltonian no. I. On the other hand, intermolecular interactions can also be described as effects that are mediated exclusively through a classical one-body E field without any quantum effects at all (assuming we ignore electronic exchange); we will call this Hamiltonian no. II. Moreover, one can also mix these two different Hamiltonians into a third, hybrid Hamiltonian, which preserves quantum electron-electron correlations for lower excitations but describes higher excitations in a mean-field way. To investigate which semiclassical scheme is most reliable for practical use, here we study the real-time dynamics of a minimalistic many-site model—a pair of identical two-level systems (TLSs)—undergoing either resonance energy transfer (RET) or collectively driven dynamics. While both approaches (no. 1 and no. 2) perform reasonably well when there is no strong external excitation, we find that no single approach is perfectmore » for all conditions (and all methods fail when a strong external field is applied). Each method has its own distinct problems: Hamiltonian no. I performs best for RET but behaves in a complicated manner for driven dynamics; Hamiltonian no. II is always stable, but obviously fails for RET at short distances. One key finding is that, for externally driven dynamics, a full configuration-interaction description of Hamiltonian no. I strongly overestimates the long-time electronic energy, highlighting the not obvious fact that, if one plans to merge quantum molecules with classical light, a full, exact treatment of electron-electron correlations can actually lead to worse results than a simple mean-field electronic structure treatment. Future work will need to investigate (i) how these algorithms behave in the context of more than a pair of TLSs and (ii) whether or not these algorithms can be improved in general by including crucial aspects of spontaneous emission.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1595484
Alternate Identifier(s):
OSTI ID: 1656841
Grant/Contract Number:  
SC0019397; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 100; Journal Issue: 6; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Light-matter interaction; Strong electromagnetic field effects

Citation Formats

Li, Tao E., Chen, Hsing-Ta, Nitzan, Abraham, and Subotnik, Joseph E. Understanding the nature of mean-field semiclassical light-matter dynamics: An investigation of energy transfer, electron-electron correlations, external driving, and long-time detailed balance. United States: N. p., 2019. Web. doi:10.1103/PhysRevA.100.062509.
Li, Tao E., Chen, Hsing-Ta, Nitzan, Abraham, & Subotnik, Joseph E. Understanding the nature of mean-field semiclassical light-matter dynamics: An investigation of energy transfer, electron-electron correlations, external driving, and long-time detailed balance. United States. https://doi.org/10.1103/PhysRevA.100.062509
Li, Tao E., Chen, Hsing-Ta, Nitzan, Abraham, and Subotnik, Joseph E. Fri . "Understanding the nature of mean-field semiclassical light-matter dynamics: An investigation of energy transfer, electron-electron correlations, external driving, and long-time detailed balance". United States. https://doi.org/10.1103/PhysRevA.100.062509. https://www.osti.gov/servlets/purl/1595484.
@article{osti_1595484,
title = {Understanding the nature of mean-field semiclassical light-matter dynamics: An investigation of energy transfer, electron-electron correlations, external driving, and long-time detailed balance},
author = {Li, Tao E. and Chen, Hsing-Ta and Nitzan, Abraham and Subotnik, Joseph E.},
abstractNote = {Semiclassical electrodynamics (with quantum matter plus classical electrodynamics fields) is an appealing approach for studying light-matter interactions, especially for realistic molecular systems. However, there is no unique semiclassical scheme. On the one hand, intermolecular interactions can be described instantaneously by static two-body interactions connecting two different molecules, while a classical transverse E field acts as a spectator at short distance; we will call this Hamiltonian no. I. On the other hand, intermolecular interactions can also be described as effects that are mediated exclusively through a classical one-body E field without any quantum effects at all (assuming we ignore electronic exchange); we will call this Hamiltonian no. II. Moreover, one can also mix these two different Hamiltonians into a third, hybrid Hamiltonian, which preserves quantum electron-electron correlations for lower excitations but describes higher excitations in a mean-field way. To investigate which semiclassical scheme is most reliable for practical use, here we study the real-time dynamics of a minimalistic many-site model—a pair of identical two-level systems (TLSs)—undergoing either resonance energy transfer (RET) or collectively driven dynamics. While both approaches (no. 1 and no. 2) perform reasonably well when there is no strong external excitation, we find that no single approach is perfect for all conditions (and all methods fail when a strong external field is applied). Each method has its own distinct problems: Hamiltonian no. I performs best for RET but behaves in a complicated manner for driven dynamics; Hamiltonian no. II is always stable, but obviously fails for RET at short distances. One key finding is that, for externally driven dynamics, a full configuration-interaction description of Hamiltonian no. I strongly overestimates the long-time electronic energy, highlighting the not obvious fact that, if one plans to merge quantum molecules with classical light, a full, exact treatment of electron-electron correlations can actually lead to worse results than a simple mean-field electronic structure treatment. Future work will need to investigate (i) how these algorithms behave in the context of more than a pair of TLSs and (ii) whether or not these algorithms can be improved in general by including crucial aspects of spontaneous emission.},
doi = {10.1103/PhysRevA.100.062509},
url = {https://www.osti.gov/biblio/1595484}, journal = {Physical Review A},
issn = {2469-9926},
number = 6,
volume = 100,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Nonlinear nanopolaritonics: Finite-difference time-domain Maxwell–Schrödinger simulation of molecule-assisted plasmon transfer
journal, July 2009


Light-matter interactions via the exact factorization approach
journal, August 2018


Molecular nanopolaritonics: Cross manipulation of near-field plasmons and molecules. I. Theory and application to junction control
journal, October 2007


Radiation from an N -Atom System. I. General Formalism
journal, September 1970


Quantum local-field corrections and spontaneous decay
journal, August 1999


Implementation of the time-dependent configuration-interaction singles method for atomic strong-field processes
journal, August 2010


Superradiance: An essay on the theory of collective spontaneous emission
journal, December 1982


Fundamental figures of merit for engineering Förster resonance energy transfer
journal, January 2018


Ultrafast pulse interactions with two-level atoms
journal, October 1995


Theoretical analysis of dipole-induced electromagnetic transparency
journal, April 2015


Strong coupling between surface plasmon polaritons and emitters: a review
journal, December 2014


Dipole-Induced Electromagnetic Transparency
journal, October 2014


Atoms and molecules in cavities, from weak to strong coupling in quantum-electrodynamics (QED) chemistry
journal, March 2017


Ab initio simulations of light propagation in silver cluster nanostructures
journal, January 2014


Geometric anisotropic effects on local field distribution: Generalized Clausius–Mossotti relation
journal, December 2001


A Necessary Trade-off for Semiclassical Electrodynamics: Accurate Short-Range Coulomb Interactions versus the Enforcement of Causality?
journal, September 2018


Quantum Beats from Entangled Localized Surface Plasmons
journal, January 2015


Theory for polariton-assisted remote energy transfer
journal, January 2018


A strongly interacting polaritonic quantum dot
journal, March 2018


Single-particle model of a strongly driven, dense, nanoscale quantum ensemble
journal, January 2018


Mediation of resonance energy transfer by a third molecule
journal, January 2012


Ehrenfest+R dynamics. I. A mixed quantum–classical electrodynamics simulation of spontaneous emission
journal, January 2019


Time-dependent configuration-interaction calculations of laser-pulse-driven many-electron dynamics: Controlled dipole switching in lithium cyanide
journal, August 2005


Radiative Effects in Semiclassical Theory
journal, March 1969


Zwischenmolekulare Energiewanderung und Fluoreszenz
journal, January 1948


Mixed quantum-classical electrodynamics: Understanding spontaneous decay and zero-point energy
journal, March 2018


A classical/semiclassical theory for the interaction of infrared radiation with molecular systems
journal, September 1978


Modification of excitation and charge transfer in cavity quantum-electrodynamical chemistry
journal, February 2019


Multiscale Maxwell–Schrödinger modeling: A split field finite-difference time-domain approach to molecular nanopolaritonics
journal, March 2009


Capturing vacuum fluctuations and photon correlations in cavity quantum electrodynamics with multitrajectory Ehrenfest dynamics
journal, June 2019


Time-dependent configuration-interaction calculations of laser-driven dynamics in presence of dissipation
journal, August 2008