Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00638892" target="_blank" >RIV/61388955:_____/25:00638892 - isvavai.cz</a>

Alternative codes found

RIV/00216208:11320/25:10512236

Result on the web

<a href="https://hdl.handle.net/11104/0369447" target="_blank" >https://hdl.handle.net/11104/0369447</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.5c00927" target="_blank" >10.1021/acs.jctc.5c00927</a>

Result language

angličtina

Original language name

Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

Original language description

The description of strongly correlated systems interacting with quantized cavity modes poses significant theoretical challenges due to the combinatorial scaling of the electronic and photonic degrees of freedom. Recent advances addressing this complexity include cavity quantum electrodynamics (QED) generalizations of complete active space configuration interaction and density matrix renormalization group methods. In this work, we introduce a QED extension of state-averaged complete active space self-consistent field theory, which incorporates cavity-induced correlations through a second-order orbital optimization framework with robust convergence properties. The method is implemented using both photon number state and coherent state representations, with the latter showing robust origin invariance in the energies, regardless of the completeness of the photonic Fock space. The implementation enables symmetry-free orbital relaxations to account for photon-mediated symmetry breaking in polaritonic systems. Numerical validation on lithium hydride, hydroxide anion, and magnesium hydride cation demonstrates that this method achieves significantly improved accuracy in modeling ground-state and polariton potential energy surfaces compared with QED-CASCI in a fixed orbital basis. In these studies, we reach sub kcal/mol accuracy in potential energy surface in much smaller active spaces than are required for QED-CASCI. This advancement provides a more robust approach for studying cavity-altered chemical landscapes for ground and excited strongly coupled systems.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2025

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Volume of the periodical

21

Issue of the periodical within the volume

18

Country of publishing house

US - UNITED STATES

Number of pages

11

Pages from-to

8812-8822

UT code for WoS article

001560912900001

EID of the result in the Scopus database

2-s2.0-105016546001