The Role of Strong Coupling in the Process of Photobleaching Suppression

Abstract

We theoretically study the role of strong coupling between an organic J-aggregated chromophore and a plasmonic nanostructure in the process of photobleaching suppression. We take into account the influence of vibrational degrees of freedom of nuclei in the molecules of J-aggregates in the Born–Markov approximation. We then show that in the strong coupling regime in this system, the stability of the J-aggregated chromophore increases by an order of magnitude. We also show that there is an optimal value of red detuning between the plasmon resonance frequency and the frequency of the dipole transition in the J-aggregate, for which the photobleaching suppression is most pronounced. We find this optimal value at different Rabi frequencies. Our results clarify the role of strong coupling between a plasmon structure near field and a molecular dipole moment in the process of photobleaching suppression and they pave the way for control of a chemical reaction in the vicinity of a plasmonic nanostructure.

Abundance of cavity-free polaritonic states in resonant materials and nanostructures

“…Several experimental studies show that strong coupling can affect photo-chemical processes, [5][6][7] and these results are essentially in agreement with theoretical descriptions. [8][9][10][11][12][13][14] Thermally activated ground-state chemical reactions in the vibrational strong coupling (VSC) regime seem to be more controversial. In this case, just a few experimental reports exist, [15][16][17][18] and there is far less conclusive agreement with theory.…”

Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry

“…Notably, cavity decay (photon leakage from the cavity) can enable the suppression of photodegradation by diverting population from polaritons to the electronic ground state instead of to the product. [40][41][42] The effect of cavity decay on photochemical reactivity has also been demonstrated theoretically for photodissociation 43,44 and photoisomerization 38,39 . Another contributor to the suppression of photodegradation is the relaxation between polaritons and dark states.…”

“…Another contributor to the suppression of photodegradation is the relaxation between polaritons and dark states. 40,42 This dissipative coupling can even mediate polariton-assisted remote energy transfer. [45][46][47][48][49] Much less is understood about the ability to modify thermally activated reactions using SC 50,51 of molecular vibrations, commonly known as vibrational SC (VSC).…”

Strong-coupling-assisted formation of coherent radiation below the lasing threshold

“…In this strong coupling regime, the interaction between the EM field and the atoms or molecules results in the formation of hybrid polaritonic states and the appearance of Rabi splitting in the system spectrum [7][8][9][10][11]. This formation of hybrid states leads to changes in the optical [13,14], electrical [15,16] and chemical [17][18][19] properties of the medium, which can be used, for example, to control the chemical reactions [18][19][20] or to tune the electrical conductivity [15] and work function [16]. Strongly coupled light-matter systems show promise for the development of polariton circuits [21], single-photon switches [22,23] and all-optical logic elements [13].…”