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This paper extends the spin-flip configuration interaction singles (SF-CIS) method to explicitly include quantized cavity photons, creating the QED-SF-CIS method for modeling strong static correlation in quantum electrodynamics. The authors derive the spin-flip Hamiltonian, demonstrating the necessity of including the double excitation subspace to accurately describe singlet electronic states interacting with cavity photons. Through molecular examples, they show how cavity coupling can provide additional tunability in bond-breaking processes and generalize the approach to include higher numbers of photonic excitations for strong coupling regimes.
Cavity quantum electrodynamics offers a new knob for tuning bond-breaking processes in molecular materials, as demonstrated by a new method that explicitly includes quantized cavity photons in spin-flip configuration interaction calculations.
In computational chemistry of molecular materials, strong static correlation effects appear when electronic states, often involving the ground state, become quasi-degenerate, as occurs, for example, in bond-breaking processes. Such situations present significant challenges for accurate theoretical treatment. In these regimes, many-body methods involving a single-determinant description, such as Hartree-Fock theory and its time-dependent extension, fail to reproduce the correct topology of the ground and excited state potential energy surfaces (e.g., near conical intersections). When strongly correlated electronic systems are further strongly coupled to a quantized radiation field within the framework of non-relativistic cavity quantum electrodynamics, an additional photonic degree of freedom introduces both new complexity and new opportunities to control. Excited cavity photons can modify bond-breaking processes and enable tunability of geometrical and spin-phase transitions, for instance, in organometallic complexes. To overcome this bottleneck, in this work, we extend the well-studied spin-flip configuration interaction singles (SF-CIS) approach to explicitly include quantized cavity photons leading to QED-SF-CIS method. We derive the spin-flip Hamiltonian and find that the double excitation subspace of the system (single with respect to electronic excitation) must be included in the configurations to properly describe singlet electronic states interacting with cavity photons. We then illustrate, through representative molecular examples, how cavity coupling can provide additional tunability in bond-breaking processes. We finally generalize this approach to include higher numbers of photonic excitations, which are required in the strong coupling regime.
