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.
This content will become publicly available on November 21, 2025
Experimental demonstrations of modified chemical structure and reactivity under strong light–matter coupling have spurred theoretical and computational efforts to uncover underlying mechanisms. Ab initio cavity quantum electrodynamics (QED) combines quantum chemistry with cavity QED to investigate these phenomena in detail. Unitary transformations of ab initio cavity QED Hamiltonians have been used to make them more computationally tractable. We analyze one such transformation, the coherent state transformation, using perturbation theory. Applying perturbation theory up to third order for ground state energies and potential energy surfaces of several molecular systems under electronic strong coupling, we show that the coherent state transformation yields better agreement with exact ground state energies. We examine one specific case using perturbation theory up to ninth order and find that coherent state transformation performs better up to fifth order but converges more slowly to the exact ground state energy at higher orders. In addition, we apply perturbation theory up to second order for cavity mode states under bilinear coupling, elucidating how the coherent state transformation accelerates the convergence of the photonic subspace toward the complete basis limit and renders molecular ion energies origin invariant. These findings contribute valuable insights into computational advantages of the coherent state transformation in the context of ab initio cavity quantum electrodynamics methods.
more » « less- PAR ID:
- 10558029
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 161
- Issue:
- 19
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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