2026-04-02 パシフィック・ノースウェスト国立研究所（PNNL）
New theoretical and modeling approaches enable simulation of systems of molecules inside cavities.(Image by Nathan Johnson | Pacific Northwest National Laboratory)
＜関連情報＞
- https://www.pnnl.gov/publications/advancing-predictive-theories-cavity-modulated-molecular-systems
- https://pubs.acs.org/doi/full/10.1021/acs.jctc.5c01599
- https://pubs.acs.org/doi/10.1021/acs.jpclett.5c02285
- https://pubs.acs.org/doi/10.1021/acs.jctc.5c00927
量子電磁力学結合クラスター大規模計算：複雑系向け高性能実装 Quantum Electrodynamics Coupled-Cluster at Scale: High-Performance Implementation for Complex Systems
Nicholas P. Bauman,Himadri Pathak,Marcus D. Liebenthal,Ajay Panyala,Daniel Mejia-Rodriguez,Niranjan Govind,and Karol Kowalski
Journal of Chemical Theory and computation Published December 15, 2025
DOI:https://doi.org/10.1021/acs.jctc.5c01599
Abstract
Coupled-cluster theory (CC) is a highly accurate and versatile method for simulating complex interactions within quantum systems. The extension of CC theory to model mixed electron-photon processes with quantum electrodynamics (QED) has improved our capability to predict cavity-modified chemistry, a field where photons are used as cost-effective and eco-friendly alternatives to catalyze/inhibit chemical reactions. However, calculations with CC methods, even without incorporating QED effects, are often prohibitively expensive. Simulations of larger systems require scalable infrastructures that exist for traditional CC methods but not for QED-CC methods. As such, we present a GPU-enabled, high-performance, open-source implementation of the quantum electrodynamics coupled-cluster method with single and double excitations (QED-CCSD) within the ExaChem quantum chemistry software package. ExaChem relies on the Tensor Algebra for Many-body Methods (TAMM) infrastructure: a parallel heterogeneous tensor library designed to achieve scalable performance on modern heterogeneous supercomputing platforms. We discuss theoretical foundations, algorithmic details, and numerical benchmarks to showcase the larger systems that ExaChem can simulate and how the integration of photonic degrees-of-freedom alters their ground-state properties.
強結合光物質系におけるキャビティ依存交換相関相互作用に対するメタ一般化勾配近似 A Meta-Generalized Gradient Approximation for the Cavity-Dependent Exchange-Correlation Interaction in Strongly Coupled Light–Matter Systems
Daniel Mejia-Rodriguez,and Niranjan Govind
The Journal of Physical Chemistry Letters Published: December 15, 2025
DOI:https://doi.org/10.1021/acs.jpclett.5c02285
Abstract
Strong light–matter coupling in optical cavities enables the manipulation of chemical and physical properties without altering molecular composition. Theoretical modeling of such phenomena requires exchange-correlation (XC) functionals that account for both electron–electron and electron–photon (ep) interactions within quantum electrodynamical density functional theory (QEDFT). In this work, we develop a meta-generalized gradient approximation (meta-GGA) specifically targeting the cavity-dependent XC interaction in strongly coupled light–matter systems. This novel approximation is built upon a new semilocal polarizability approximation, which draws from the jellium-with-a-gap model, and can be extended to a “global hybrid” variant that goes beyond the isotropic model from previous approximations. The polarizability model yields significantly improved dispersion coefficients and benchmark calculations with the cavity-dependent XC functional demonstrate improved agreement with QED Hartree–Fock (QED-HF) reference energies. Application to the regioselectivity of brominated nitrobenzene intermediates reveals the functional’s capacity to capture cavity-induced energetic shifts. Our results advance the Jacob’s ladder of functionals for QEDFT and provide a practical tool for modeling polaritonic chemistry.
相関系における強い光物質結合のモデリング：状態平均キャビティ量子電磁力学完全活性空間自己無撞着場理論 Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory
Nam Vu,Kenny Ampoh,Mikuláš Matoušek,Libor Veis,Niranjan Govind,and Jonathan J. Foley IV
Journal of Chemical Theory and Computation Published August 30, 2025
DOI:https://doi.org/10.1021/acs.jctc.5c00927
Abstract
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.
