Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction Theory

01 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Polariton chemistry has attracted great attention as a potential route to modify chemical structure, properties, and reactivity through strong interactions between molecular electronic, vibrational, or rovibrational degrees of freedom. A rigorous theoretical treatment of molecular polaritons requires the treatment of matter and photon degrees of freedom on equal quantum mechanical footing. In the limit of molecular electronic strong or ultrastrong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach we refer to as ab initio cavity quantum electrodynamics, where the photon degrees of freedom are treated at the level of cavity quantum electrodynamics. Here, we present an approach called Cavity Quantum Electrodynamics Complete Active Space Configuration Interaction theory to provide ground- and excited-state polaritonic surfaces with a balanced description of strong correlation effects among electronic and photonic degrees of freedom. This method provides a platform for ab initio cavity quantum electrodynamics when both strong electron correlation and strong light-matter coupling are important, and is an important step towards computational approaches that yield multiple polaritonic potential energy surfaces and couplings that can be leveraged for {ab initio molecular dynamics simulations of polariton chemistry.


Quantum Chemistry
Polaritonic Chemistry
Strong Coupling
Strong Correlation

Supplementary weblinks


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.