Theory for Nonlinear Spectroscopy of Vibrational Polaritons

Ribeiro, Raphael F.; Dunkelberger, Adam D.; Xiang, Bo; Xiong, Wei; Simpkins, Blake S.

doi:10.1021/acs.jpclett.8b01176

Cited by 95 publications

(149 citation statements)

References 60 publications

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“…Similarly to the previous fast bath scenario, our calculations reveal two qualitatively different pictures of the population dynamics in the polaron frame depending on the magnitude of Ω. For sufficiently weak light-matter coupling, the initial state is comprised of approximately equally populated lower and upper dark state manifolds since |c (20) and Fig. 1b-I], a consequence of the prevalence of the electronic coupling V ST over the weak coupling of the R-ISC transition to the phonon environment.…”

Section: Resultssupporting

confidence: 63%

Triplet harvesting in the polaritonic regime: A variational polaron approach

Martínez-Martínez

Eizner

Kéna‐Cohen

et al. 2019

The Journal of Chemical Physics

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We explore the electroluminescence efficiency for a quantum mechanical model of a large number of molecular emitters embedded in an optical microcavity. We characterize the circumstances under which a microcavity enhances harvesting of triplet excitons via reverse intersystem-crossing (R-ISC) into singlet populations that can emit light. For that end, we develop a time-local master equation in a variationally optimized frame which allows for the exploration of the population dynamics of chemically relevant species in different regimes of emitter coupling to the condensed phase vibrational bath and to the microcavity photonic mode. For a vibrational bath that equilibrates faster than R-ISC (in emitters with weak singlet-triplet mixing), our results reveal that significant improvements in efficiencies with respect to the cavity-free counterpart can be obtained for strong coupling of the singlet exciton to a photonic mode, as long as the singlet to triplet exciton transition is within the inverted Marcus regime; under these circumstances, the activation energy barrier from the triplet to the lower polariton can be greatly reduced with respect to that from the triplet to the singlet exciton, thus overcoming the detrimental delocalization of the polariton states across a macroscopic number of molecules. On the other hand, for a vibrational bath that equilibrates slower than R-ISC (i.e., emitters with strong singlet-triplet mixing), we find that while enhancemnents in photoluminiscence can be obtained via vibrational relaxation into polaritons, this only occurs for small number of emitters coupled to the photon mode, with delocalization of the polaritons across many emitters eventually being detrimental to electroluminescence efficiency. These findings provide insight on the tunability of optoelectronic processes in molecular materials due to weak and strong light-matter coupling.arXiv:1904.07948v1 [cond-mat.mes-hall]

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Section: Resultssupporting

confidence: 63%

Triplet harvesting in the polaritonic regime: A variational polaron approach

Martínez-Martínez

Eizner

Kéna‐Cohen

et al. 2019

The Journal of Chemical Physics

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“…[ [166][167][168][169] ESC Polariton condensation and lasing with vibronic transitions in molecular ensembles. [170,171] ESC Few-photon nonlinear quantum optics with molecular ensembles.…”

Section: A Recent Experimental Progressmentioning

confidence: 99%

Molecular polaritons for controlling chemistry with quantum optics

Herrera

Owrutsky

2020

The Journal of Chemical Physics

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248

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This is a tutorial-style introduction to the field of molecular polaritons. We describe the basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities. Using a microscopic quantum electrodynamics formulation, we discuss the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo, including chemical reactions. We highlight some of the observable consequences of this competition between local and collective effects in linear transmission spectroscopy, including the formal equivalence between quantum mechanical theory and the classical transfer matrix method, under specific conditions of molecular density and indistinguishability. We also overview recent experimental and theoretical developments on strong and ultrastrong coupling with electronic and vibrational transitions, with a special focus on cavity-modified chemistry and infrared spectroscopy under vibrational strong coupling. We finally suggest several opportunities for further studies that may lead to novel applications in chemical and electromagnetic sensing, energy conversion, optoelectronics, quantum control and quantum technology.

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“…In this section, we show that the measured nonlinear signals obtained from the LP and UP (25 μm system) 2D IR spectral cuts at zero waiting-time cannot be reproduced with a simple spectral fitting based on previous studies (6,13,14). A two-component spectral fitting was applied to the LP/UP spectral cuts of 2D-IR spectrum of 25-μm system at t2 = 0 ps, using the following equation…”

Section: S25 Two-component Spectral Fitting Of Absorptive Pump-probementioning

confidence: 99%

“…This interplay between microscopic and macroscopic characteristics is at the heart of the versatility of polaritons. Much of the recent research on molecular polaritons has focused on the modification of molecular properties through the interaction with an optical cavity (5)(6)(7)(8)(9)(10)(11)(12)(13)(14). Conversely, control of polariton optical response via manipulation of the macroscopic parameters which define the electromagnetic modes (e.g., cavity length) has received far less attention (15) (Fig.1a) and, in fact, we are not aware of any investigations of these effects in the nonlinear photonic regime.…”

Section: Introductionmentioning

confidence: 99%

Manipulating optical nonlinearities of molecular polaritons by delocalization

et al. 2019

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Optical nonlinearities are key resources in the contemporary photonics toolbox, relevant to quantum gate operations and all-optical switches. Chemical modification is often employed to control the nonlinear response of materials at the microscopic level, but on-the-fly manipulation of such response is challenging. Tunability of optical nonlinearities in the mid-IR is even less developed, hindering its applications in chemical sensing or IR photonic circuitry. Here, we report control of vibrational polariton coherent nonlinearities by manipulation of macroscopic parameters such as cavity longitudinal length or molecular concentration. Further 2D IR investigations reveal that nonlinear dephasing provides the dominant source of the observed ultrafast polariton nonlinearities. The reported phenomena originate from the nonlinear macroscopic polarization stemming from strong coupling between microscopic molecular excitations and a macroscopic photonic cavity mode. RESULTS. Polariton bleach dependence on cavity longitudinal length.To investigate the optical nonlinearities of vibrational polaritons, we measure their third-order nonlinear susceptibilities by femtosecond IR pumpprobe spectroscopy. The hybrid light-matter system consists of a FP microcavity filled with an ensemble of asymmetric carbonyl stretch modes originating from W(CO)6 molecules in a hexane solution (14). At zero waiting time, when IR pump and probe pulses overlap, we see a notable reduction in the intensity of the polariton transmission (Figs. 1b). This reduction gives rise to absorptive features in the differential transmission spectra (Figs. 1c). Qualitatively, the observed behavior resembles the well-known "photon blockade effect" in the single-emitter quantum regime of the Jaynes-Cummings model (18)(19)(20): when a photon excites the emitter-cavity system, the latter is blocked from further interactions with incoming photons of the same frequency. Here, we observe a similar effect, although it is in the ensemble regime and the mechanism for reduced transmission is quite different from the single oscillator case. We hereafter term this phenomenon "polariton bleach". Note this effect is not a trivial coherent artifact from the overlap between the pump and probe pulses. The IR pulse duration is ~100 fs, while the bleach lasts for less than 5 ps (which is also the approximate lifetime of the cavity photon), indicating the effect is intrinsic to the lifetime of the cavity polaritons. The polariton bleach concept provides a foundation for developing mid-IR photonic devices in the ensemble regime of light-matter strong coupling. Chen for his help on designing Figure 1 and Jiaxi Wang for her help on the experiments.

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Theory for Nonlinear Spectroscopy of Vibrational Polaritons

Cited by 95 publications

References 60 publications

Triplet harvesting in the polaritonic regime: A variational polaron approach

Triplet harvesting in the polaritonic regime: A variational polaron approach

Molecular polaritons for controlling chemistry with quantum optics

Manipulating optical nonlinearities of molecular polaritons by delocalization

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