Yassir El Moutaoukal, Rosario R Riso, Matteo Castagnola, Enrico Ronca, Henrik Koch
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引用次数: 0
Abstract
Perturbative approaches are methods to efficiently tackle many-body problems, offering both intuitive insights and analysis of correlation effects. However, their application to systems where light and matter are strongly coupled is nontrivial. Specifically, the definition of suitable orbitals for the zeroth-order Hamiltonian represents a significant theoretical challenge. While reviewing previously investigated orbital choices, this work presents an alternative polaritonic orbital basis suitable for the strong coupling regime. We develop a quantum electrodynamical (QED) Møller-Plesset perturbation theory using orbitals obtained from the strong coupling QED Hartree-Fock. We assess the strengths and limitations of the different approaches with emphasis on frequency and coupling strength dispersions, intermolecular interactions and polarization orientational effects. The results show the essential role of using a consistent molecular orbital framework in order to achieve an accurate description of cavity-induced electron-photon correlation effects.
期刊介绍：
The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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