Cavity quantum-electrodynamical time-dependent density functional theory within Gaussian atomic basis. II. Analytic...

Area of Science:

• Computational Chemistry
• Quantum Electrodynamics
• Spectroscopy

Background:

• Cavity quantum electrodynamics (cQED) models describe light-matter interactions in confined spaces.
• Time-dependent density functional theory (TDDFT) is widely used for electronic excited states.
• Previous cQED-TDDFT models laid the groundwork for this study.

Purpose of the Study:

• To derive and implement analytic energy gradients for polaritonic states within cQED-TDDFT.
• To enable efficient geometry optimization and reaction path calculations for photochromes in microcavities.
• To extend the applicability of these gradients to molecular complexes and ensembles.

Main Methods:

• Formulation of analytic energy gradients for polaritonic states.
• Implementation within the cQED-TDDFT framework.
• Application to single photochromes and molecular systems in microcavities.

Main Results:

• Successful derivation and implementation of analytic energy gradients for cQED-TDDFT polaritonic states.
• Demonstrated applicability to single photochromes and extended systems.
• Provided a computationally efficient tool for studying light-matter interactions.

Conclusions:

• The developed analytic energy gradient is a significant advancement for cQED-TDDFT.
• This method facilitates the study of photochromic systems interacting with microcavities.
• The approach offers a scalable and versatile tool for theoretical chemistry research.