An efficient and flexible approach for computing rovibrational polaritons from first principles

A theoretical framework is presented for the computation of the rovibrational polaritonic states of a molecule in a lossless infrared (IR) micro cavity. In the proposed approach, the quantum treatment of the rotational and vibrational motions of the molecule can be formulated using arbitrary approximations. The cavity-induced changes in electronic structure are treated perturbatively, which allows using the existing polished tools of standard quantum chemistry for determining electronic molecular properties. As a case study, the rovibrational polaritons and related thermodynamic properties of H2O in an IR microcavity are computed for varying cavity parameters, applying various approximations to describe the molecular degrees of freedom. The self-dipole interaction is significant for nearly all light-matter coupling strengths investigated, and the molecular polarizability proved important for the correct qualitative behavior of the energy level shifts induced by the cavity. On the other hand, the magnitude of polarization remains small, justifying the perturbative approach for the cavity-induced changes in electronic structure. Comparing results obtained using a high-accuracy variational molecular model with those obtained utilizing the rigid rotor and harmonic oscillator approximations revealed that as long as the rovibrational model is appropriate for describing the field-free molecule, the computed rovibropolaritonic properties can be expected to be accurate as well. Strong light-matter coupling between the radiation mode of an IR cavity and the rovibrational states of H2O leads to minor changes in the thermodynamic properties of the system, and these changes seem to be dominated by non-resonant interactions between the quantum light and matter.

Automated summary

A theoretical framework is proposed for calculating the rovibrational polaritonic states of a molecule in an infrared microcavity. The rotational and vibrational motions of the molecule are treated quantum mechanically using arbitrary approximations. Changes in electronic structure induced by the cavity are treated perturbatively, making use of standard quantum chemistry tools. The study shows that the self-dipole interaction and molecular polarizability are important for accurate energy level shifts induced by the cavity, while the magnitude of polarization remains small, justifying the perturbative approach.