Quantum-Electrodynamical Time-Dependent Density Functional Theory Description of Molecules in Optical Cavities
We introduce a quantum-electrodynamical time-dependent density functional theory with a tensor-product representation (QED-TDDFT-TP) to model molecules strongly coupled to quantized cavity fields. By combining real-space electronic wave functions with truncated Fock-space photon states, the method captures light-matter correlations at a computational cost close to standard DFT. Benchmark calculations show good agreement with QED-FCI and QED-CASCI for ground-state energies and polaritonic spectra. Applications to weakly bound dimers─including (H<sub>2</sub>)<sub>2</sub>, Ar<sub>2</sub>, (H<sub>2</sub>O)<sub>2</sub>, and HF─demonstrate that cavity confinement can significantly alter binding energies and geometries in a polarization-dependent manner. The framework provides an accurate and scalable tool for studying cavity-modified molecular structure and interactions.
Authors
- Cody Covington (ORCID: https://orcid.org/0009-0009-7154-9475)
- Yetmgeta S. Aklilu
- Matthew Shepherd
- Kalman Varga
Institutions
- Austin Peay State University (US)
- Vanderbilt University (US)
- Auburn University (US)
Publication Details
- Journal
- Journal of Chemical Theory and Computation
- Published
- 2026-02-15
- DOI
- https://doi.org/10.1021/acs.jctc.5c01973
- Primary Topic
- Strong Light-Matter Interactions
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Science Foundation
- Division of Materials Research
- Office of Advanced Cyberinfrastructure