Three-player polaritons: nonadiabatic fingerprints in an entangled atom–molecule–photon system

Abstract

A quantum system composed of a molecule and an atomic ensemble, confined in a microscopic cavity, is investigated theoretically. The indirect coupling between atoms and the molecule, realized by their interaction with the cavity radiation mode, leads to a coherent mixing of atomic and molecular states, and at strong enough cavity field strengths hybrid atom-molecule-photon polaritons are formed. It is shown for the Na 2 molecule that by changing the cavity wavelength and the atomic transition frequency, the potential energy landscape of the polaritonic states and the corresponding spectrum could be changed significantly. Moreover, an unforeseen intensity borrowing effect, which can be seen as a strong nonadiabatic fingerprint, is identified in the atomic transition peak, originating from the contamination of the atomic excited state with excited molecular rovibronic states.

Nonadiabatic phenomena in molecular vibrational polaritons

“…Fig. 1 demonstrates that in the case of the two different isotopologues, three polaritons are formed, as expected [45,65], and conical intersections (CI) can be formed between the VPESs. In the case of two identical H 35 Cl molecules, Fig.…”

“…Another physical property which can be effected by CIs or LICIs is the spectrum. The spectroscopy of polaritonic systems is a valuable tool for providing insight into their various physiochemical properties [21,45,73,74], and nonadiabatic effects resulting from the strong coupling of the electronic, vibrational, rotational, and photonic degrees of freedom can cause a significant modification on the molecular absorption spectra. In one possible theoretical formulation of light-dressed spectroscopy [75], transitions between lightdressed states are evaluated using first-order time-dependent perturbation theory, that is, for the T l←k transition amplitude between the k th and l th light-dressed state T l←k ∝…”

“…In the first situation the different electronic molecular states mix with the UV-visible cavity photon forming hybrid light-matter, so-called electronic or vibronic polariton states carrying both characters of matter and light. Several experimental and theoretical studies have demonstrated that this phenomenon gives rise to a variety of interesting effects such as modification of the chemical landscapes [5,6,9,18], cavity-induced nonadiabatic phenomena [3,8,10,[14][15][16][21][22][23][24][25][26], controlling photochemistry [14,15,17,19,20,26] , or intermolecular collective effects [17,[42][43][44][45].…”

Nonadiabatic phenomena in molecular vibrational polaritons

“…Fig. 2 demonstrates that in the case of the two different isotopologues, three bright polaritons are formed, as expected [28,53], and conical intersections (CI) can be formed between the VPESs. In the case of two identical H 35 Cl molecules, Fig.…”

Catalysis by Dark States in Vibropolaritonic Chemistry

“…The molecule undergoes nonadiabatic intramolecular electron transfer, and a cavity mode interacts collectively with a reactive vibrational mode and N − 1 nonreactive vibrational modes. The model here considered is general enough that it should also be applicable to the case of "solvent-assisted VSC" [46][47][48][49].…”