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- Schnappinger, Thomas, et al.
(författare)
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Cavity Born–Oppenheimer Hartree–Fock Ansatz : Light–Matter Properties of Strongly Coupled Molecular Ensembles
- 2023
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Ingår i: The Journal of Physical Chemistry Letters. - 1948-7185. ; 14:36, s. 8024-8033
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Tidskriftsartikel (refereegranskat)abstract
- Experimental studies indicate that optical cavities can affect chemical reactions through either vibrational or electronic strong coupling and the quantized cavity modes. However, the current understanding of the interplay between molecules and confined light modes is incomplete. Accurate theoretical models that take into account intermolecular interactions to describe ensembles are therefore essential to understand the mechanisms governing polaritonic chemistry. We present an ab initio Hartree–Fock ansatz in the framework of the cavity Born–Oppenheimer approximation and study molecules strongly interacting with an optical cavity. This ansatz provides a nonperturbative, self-consistent description of strongly coupled molecular ensembles, taking into account the cavity-mediated dipole self-energy contributions. To demonstrate the capability of the cavity Born–Oppenheimer Hartree–Fock ansatz, we study the collective effects in ensembles of strongly coupled diatomic hydrogen fluoride molecules. Our results highlight the importance of the cavity-mediated intermolecular dipole–dipole interactions, which lead to energetic changes of individual molecules in the coupled ensemble.
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| 2. |
- Sidler, Dominik, et al.
(författare)
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A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
- 2022
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 1089-7690 .- 0021-9606. ; 156:23
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Tidskriftsartikel (refereegranskat)abstract
- This Perspective provides a brief introduction into the theoretical complexity of polaritonic chemistry, which emerges from the hybrid nature of strongly coupled light-matter states. To tackle this complexity, the importance of ab initio methods is highlighted. Based on those, novel ideas and research avenues are developed with respect to quantum collectivity, as well as for resonance phenomena immanent in reaction rates under vibrational strong coupling. Indeed, fundamental theoretical questions arise about the mesoscopic scale of quantum-collectively coupled molecules when considering the depolarization shift in the interpretation of experimental data. Furthermore, to rationalize recent findings based on quantum electrodynamical density-functional theory (QEDFT), a simple, but computationally efficient, Langevin framework is proposed based on well-established methods from molecular dynamics. It suggests the emergence of cavity-induced non-equilibrium nuclear dynamics, where thermal (stochastic) resonance phenomena could emerge in the absence of external periodic driving. Overall, we believe that the latest ab initio results indeed suggest a paradigmatic shift for ground-state chemical reactions under vibrational strong coupling from the collective quantum interpretation toward a more local, (semi)-classically and non-equilibrium dominated perspective. Finally, various extensions toward a refined description of cavity-modified chemistry are introduced in the context of QEDFT, and future directions of the field are sketched.
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