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Molecules under strong or ultra-strong light–matter coupling present an intriguing route to modify chemical structure, properties, and reactivity. A rigorous theoretical treatment of such systems requires handling matter and photon degrees of freedom on an equal quantum mechanical footing. In the regime of molecular electronic strong or ultra-strong coupling to one or a few molecules, it is desirable to treat the molecular electronic degrees of freedom using the tools of ab initio quantum chemistry, yielding an approach referred to as ab initio cavity quantum electrodynamics (ai-QED), where the photon degrees of freedom are treated at the level of cavity QED. We analyze two complementary approaches to ai-QED: (1) a parameterized ai-QED, a two-step approach where the matter degrees of freedom are computed using existing electronic structure theories, enabling the construction of rigorous ai-QED Hamiltonians in a basis of many-electron eigenstates, and (2) self-consistent ai-QED, a one-step approach where electronic structure methods are generalized to include coupling between electronic and photon degrees of freedom. Although these approaches are equivalent in their exact limits, we identify a disparity between the projection of the two-body dipole self-energy operator that appears in the parameterized approach and its exact counterpart in the self-consistent approach. We provide a theoretical argument that this disparity resolves only under the limit of a complete orbital basis and a complete many-electron basis for the projection. We present numerical results highlighting this disparity and its resolution in a particularly simple molecular system of helium hydride cation, where it is possible to approach these two complete basis limits simultaneously. In this same helium hydride system, we examine and compare the practical issue of the computational cost required to converge each approach toward the complete orbital and many-electron bases limit. Finally, we assess the aspect of photonic convergence for polar and charged species, finding comparable behavior between parameterized and self-consistent approaches.
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Resonant light enhances phase coherence in a cavity QED simulator of fermionic superfluidity
Cavity QED experiments are natural hosts for non-equilibrium phases of matter supported by photon-mediated interactions. In this work, we consider a cavity QED simulation of the BCS model of superfluidity, by studying regimes where the cavity photons act as dynamical degrees of freedom instead of mere mediators of the interaction via virtual processes. We find an enhancement of long time coherence following a quench whenever the cavity frequency is tuned into resonance with the atoms. We discuss how this is equivalent to enhancement of non-equilibrium superfluidity and highlight similarities to an analogous phenomena recently studied in solid state quantum optics. We also discuss the conditions for observing this enhanced resonant pairing in experiments by including the effect of photon losses and inhomogeneous coupling in our analysis.
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- Award ID(s):
- 2016244
- PAR ID:
- 10341875
- Date Published:
- Journal Name:
- ArXivorg
- Issue:
- 10.48550/arXiv.2202.05851
- ISSN:
- 2331-8422
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.48550/arXiv.2202.05851
