Light–matter coupling-induced hybrid states provide the potential to tune the emission dynamics of molecular chromophores having multilevel systems. We demonstrate the alteration of delayed fluorescence dynamics by hybrid states formation through the interaction of light with a thermally activated delayed fluorescence molecule embedded in a conventional Fabry–Pérot cavity. The proximity of cavity resonance with the excited state absorption is modified by manipulating the incident angles (with sample) instead of varying the active layer thickness. The coupling-induced hybrid states are observed by angle-dependent emission spectroscopy and lifetime measurements. The variation in average emission lifetime with respect to incident angle is over 10 μs and is accompanied by significant changes in the full width at half maxima (factor of three). The control of emission via a barrier-free route or reverse intersystem crossing transition is demonstrated from these measurements. These findings suggest the possibility of tailoring intermediate states for lasing, where exciton density inversion can enhance spontaneous emission.
Light–matter coupling-induced hybrid states provide the potential to tune the emission dynamics of molecular chromophores having multilevel systems. We demonstrate the alteration of delayed fluorescence dynamics by hybrid states formation through the interaction of light with a thermally activated delayed fluorescence molecule embedded in a conventional Fabry–Pérot cavity. The proximity of cavity resonance with the excited state absorption is modified by manipulating the incident angles (with sample) instead of varying the active layer thickness. The coupling-induced hybrid states are observed by angle-dependent emission spectroscopy and lifetime measurements. The variation in average emission lifetime with respect to incident angle is over 10 μs and is accompanied by significant changes in the full width at half maxima (factor of three). The control of emission via a barrier-free route or reverse intersystem crossing transition is demonstrated from these measurements. These findings suggest the possibility of tailoring intermediate states for lasing, where exciton density inversion can enhance spontaneous emission.
In this study, we demonstrate that the fluorescence of fluorescein dye molecules can be significantly modified in both the weak and strong coupling regimes by placing the molecules inside a perturbative or non-perturbative Fabry-Pérot cavity. By controlling the cavity thickness and dye concentration, we selectively altered the frequency and number of cavity transmission peaks, thereby establishing conditions for weak or strong coupling for fluorescein molecules. Using steady-state fluorescence spectroscopy, we confirmed that both the excitation and emission spectra were substantially tuned in these coupling regimes, enabling tunable and multicolor fluorescence from a single type of dye molecule, fluorescein.
Over the last several years there has been considerable interest in the properties of atomic resonance fluorescence in an optical cavity with a primary dimension comparable to the relevant transition wavelength.1 In particular, there has been great interest in the realization of strong atom-cavity coupling2 and the suppression of spontaneous emission into "free-space" modes. However, an important but poorly understood issue relevant to low- or zero-threshold condensed phase optical devices is the nonradiative coupling of the emitting species to a thermal bath. Unlike experiments involving dilute atomic beams where the transition is well defined and broadening is negligible, coupling to a thermal bath induces spectral broadening which is usually much larger than the cavity resonance width and may often exceed the cavity mode spacing. Interesting examples of such systems are solvated dyes whose condensed phase dynamics are well known and characterized. To date, several studies have been made on fluorescence properties of solvated dyes in microcavities,3,4,5 however additional complexities such as spatial and orientational averaging have obscured to some extent the connection between radiative and nonradiative processes in such systems. We discuss the observation of spontaneous emission rate modification (both enhancement and apparent suppression) for molecular species in a microcavity where both the molecular position and transition moment orientation are well defined.6 These experiments serve as an interesting test case of molecule-cavity systems in which the emitting species is nonradiatively coupled to a thermal bath.
In this work, we investigate the influence of light-matter coupling on reaction dynamics and equilibrium properties of a single molecule inside an optical cavity. The reactive molecule is modeled using a triple-well potential, allowing two competing reaction pathways that yield distinct products. Dynamical and equilibrium simulations are performed using the numerically exact hierarchical equations of motion approach in real- and imaginary-time formulations, respectively, both implemented with tree tensor network decomposition schemes. We consider two illustrative cases: one dominated by slow kinetics and another by ultrafast processes. Our results demonstrate that the rates of ground-state reaction pathways can be selectively enhanced when the cavity frequency is tuned into resonance with a vibrational transition directly leading to the formation of the corresponding product, even when that transition is spectroscopically dark. However, tuning cavity frequency to match an absorption-dominant transition shared across both reaction pathways does not necessarily result in pronounced rate enhancements and selectivity. Together with an additional analysis using an asymmetric double-well model, we highlight the greater complexity of underlying factors governing chemical reactivity, which extend beyond considerations of transition dipole strengths and thermal population distributions that shape linear spectroscopy. Furthermore, we found that in all scenarios, the equilibrium populations remain unchanged when the molecule is moved into the cavity, regardless of the cavity frequency. Thus, our proof-of-concept study confirms at a fully quantum-mechanical level that cavity-induced modifications of chemical reactivities in resonant conditions arise from dynamical and non-equilibrium interactions between the cavity mode and molecular vibrations, rather than from the significant changes in equilibrium properties.
In this work, we investigate the influence of light-matter coupling on reaction dynamics and equilibrium properties of a single molecule inside an optical cavity. The reactive molecule is modeled using a triple-well potential, allowing two competing reaction pathways that yield distinct products. Dynamical and equilibrium simulations are performed using the numerically exact hierarchical equations of motion approach in real- and imaginary-time formulations, respectively, both implemented with tree tensor network decomposition schemes. We consider two illustrative cases: one dominated by slow kinetics and another by ultrafast processes. Our results demonstrate that the rates of ground-state reaction pathways can be selectively enhanced when the cavity frequency is tuned into resonance with a vibrational transition directly leading to the formation of the corresponding product, even when that transition is spectroscopically dark. However, tuning cavity frequency to match an absorption-dominant transition shared across both reaction pathways does not necessarily result in pronounced rate enhancements and selectivity. Together with an additional analysis using an asymmetric double-well model, we highlight the greater complexity of underlying factors governing chemical reactivity, which extend beyond considerations of transition dipole strengths and thermal population distributions that shape linear spectroscopy. Furthermore, we found that in all scenarios, the equilibrium populations remain unchanged when the molecule is moved into the cavity, regardless of the cavity frequency. Thus, our proof-of-concept study confirms at a fully quantum-mechanical level that cavity-induced modifications of chemical reactivities in resonant conditions arise from dynamical and non-equilibrium interactions between the cavity mode and molecular vibrations, rather than from the significant changes in equilibrium properties.
We investigate experimentally and theoretically the fluorescence emitted by molecular ensembles as well as spatially isolated, single molecules of an organic dye immobilized in a quasi-planar optical microresonator at room temperature. The optically excited dipole emitters couple simultaneously to on- and off-axis cavity resonances of the microresonator. The multi-spectral radiative contributions are strongly modified with respect to free (non-confined) space due to enhancement and inhibition of the molecular spontaneous emission (SpE) rate. By varying the mirror spacing of the microresonator on the nanometer-scale, the SpE rate of the cavity-confined molecules and, consequently, the spectral line width of the microresonator-controlled broadband fluorescence can be tuned by up to one order of magnitude. Stepwise reducing the optical confinement, we observe that the microresonator-controlled molecular fluorescence line shape converges towards the measured fluorescence line shape in free space. Our results are important for research on and application of broadband emitters in nano-optics and -photonics as well as microcavity-enhanced (single molecule) spectroscopy.
Harnessing strong light-matter interactions to control chemical reactions in confined electromagnetic fields offers a promising route toward deepening our understanding of chemical dynamics at the collective quantum-mechanical level, with potential implications for future chemical synthesis paradigms. Achieving this goal, however, requires an in-depth mechanistic understanding of underlying dynamical processes. As a step in this direction, we present a systematic and numerically exact quantum dynamical study of cooperative reaction dynamics inside an optical microcavity. Using a hierarchy of model systems with increasing complexity, we elucidate how cavity-modified reactivity emerges from-and is highly sensitive to-subtle structural and environmental variations. Our models consist of optically dark reactive molecules, each represented by a symmetric double well potential, coupled to infrared-active non-reactive intramolecular or solvent vibrational modes, as well as their respective dissipative environments. Our results demonstrate that cavity-induced rate modifications arise from a delicate interplay among mode hybridization in strong-coupling regimes, the dynamical balance of all participating energy exchange processes, and quantum interference between multiple fluctuation-dissipation-mediated reaction pathways enabled by collective cavity coupling. By continuously tuning a single system parameter or introducing molecular collectivity, we observe qualitatively distinct rate modification profiles as functions of the cavity frequency, including resonant rate enhancement, resonant rate suppression, hybridization-induced peak splitting, and, notably, asymmetric Fano-type line shapes in which enhancement peaks and suppression dips coexist within a narrow resonance window, highlighting the important role of quantum interference in cavity-modified chemical reactivity.