Nonadiabatic phenomena in molecular vibrational polaritons

TL;DR

This paper explores nonadiabatic effects in molecular vibrational polaritons confined in an infrared cavity, revealing conical intersections and the impact of isotopic variations on polaritonic properties.

Contribution

It uncovers conical intersections in vibrational polaritons and demonstrates how isotopic substitutions significantly influence their spectral and dynamic characteristics.

Findings

Conical intersections exist between vibrational polaritons.

Isotopic substitution alters polaritonic surfaces and couplings.

Nonadiabatic effects are crucial in modeling molecular polaritons.

Abstract

Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found. The spectral, topological, and dynamic properties of the vibrational polaritons show clear fingerprints of nonadiabatic couplings between molecular vibration, rotation and the cavity photonic mode. Furthermore, it is found that for the investigated system, composed of two rovibrating HCl molecules and the cavity mode, breaking the molecular permutational symmetry, by changing $^{35}$Cl to $^{37}$Cl in one of the HCl molecules, the polaritonic surfaces, nonadiabatic couplings, and related spectral, topological, and dynamic properties can deviate substantially. This implies that the natural occurrence of different molecular isotopologues needs to be considered when modeling realistic polaritonic systems.