اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدTheory of Vibrational Polariton Chemistry in the Collective Coupling Regime
112
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
We theoretically demonstrate that chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity-frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect is further amplified when cavity loss is considered.
قيم البحث
اقرأ أيضاً
The generation and control of exotic phenomena in organic electroluminescent microcavities, such as polariton lasing and non-linear optical effects, operating in strong and ultra-strong coupling regimes, is still a great challenge. The main obstacles
originate from the small number of molecular classes investigated as well as from the absence of an efficient strategy aiming at the maximization of polariton states population. Here we report on bright polariton organic light emitting diodes made of a coumarin fluorescent dye emitting layer, working in the ultra-strong coupling regime up to a coupling strength of 33%. Owing to a high radiative decay emission, a large Stokes shift and a fine cavity-exciton tuning, the radiative pumping mechanism of polariton states has been fully optimized, leading a large portion (25%) of the emissive electrically pumped excitons to be converted in polariton emission. The resulting polariton OLEDs showed electro-optical performances up to 0.2% of external quantum efficiency and 700 cd/m2 of luminance, corresponding to the highest values reported so far for this class of devices. Our work gives clear indications for an effective exploitation of organic polariton dynamics towards the development of novel quantum optoelectronic devices.
Time-Dependent Density Functional Theory (TDDFT) has recently been extended to describe many-body open quantum systems (OQS) evolving under non-unitary dynamics according to a quantum master equation. In the master equation approach, electronic excit
ation spectra are broadened and shifted due to relaxation and dephasing of the electronic degrees of freedom by the surrounding environment. In this paper, we develop a formulation of TDDFT linear-response theory (LR-TDDFT) for many-body electronic systems evolving under a master equation, yielding broadened excitation spectra. This is done by mapping an interacting open quantum system onto a non-interacting open Kohn-Sham system yielding the correct non-equilibrium density evolution. A pseudo-eigenvalue equation analogous to the Casida equations of usual LR-TDDFT is derived for the Redfield master equation, yielding complex energies and Lamb shifts. As a simple demonstration, we calculate the spectrum of a C$^{2+}$ atom in an optical resonator interacting with a bath of photons. The performance of an adiabatic exchange-correlation kernel is analyzed and a first-order frequency-dependent correction to the bare Kohn-Sham linewidth based on Gorling-Levy perturbation theory is calculated.
Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can be largely solved
by confining the liquid in an optical cavity under vibrational strong coupling conditions. For a liquid solution of $^{13}$CO$_2$ solute in a $^{12}$CO$_2$ solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very strong (> 3 quanta) and ultrafast (< 1 ps) excitation of the solute, all while the solvent is barely excited. By contrast, outside a cavity the same input pulse fluence can excite the solute by only half a vibrational quantum and the selectivity of excitation is low. Our finding is robust under different cavity volumes, which may lead to observable cavity enhancement on IR photochemical reactions in Fabry-Perot cavities.
For a small fraction of hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2 molecules
and a cavity mode accelerates hot-molecule relaxation. The physical mechanism underlying this acceleration is the fact that polaritons, especially the lower polariton, can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates (i) resonantly depend on the cavity mode detuning, (ii) cooperatively depend on molecular concentration or Rabi splitting, and (iii) collectively scale with the number of hot molecules, which is similar to Dickes superradiance. For larger cavity volumes, due to a balance between this superradiant-like behavior and a smaller light-matter coupling, the total VSC effect on relaxation rates can scale slower than $1/N$, and the average VSC effect per molecule can remain meaningful for up to $N sim10^4$ molecules forming VSC. Moreover, we find that the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than equally distributing it to all thermal molecules. Finally, we highlight the similarities of parameter dependence between the current finding with VSC catalysis observed in Fabry-Perot microcavities.
This work sets a road-map towards an experimental realization of strong coupling between free-electrons and photons, and analytically explores entanglement phenomena that emerge in this regime. The proposed model unifies the strong-coupling predictio
ns with known electron-photon interactions. Additionally, this work predicts a non-Columbic entanglement between freely propagating electrons. Since strong-coupling can map entanglements between photon pairs onto photon-electron pairs, it may harness electron beams for quantum communication, thus far exclusive to photons.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
