Huang-Rhys Factor Research Articles

Classification of Fungal Pigments by Simulating Their Optical Properties Using Evolutionary Optimization

Modern developments in data analysis techniques and evolutionary optimization algorithms have made it possible to analyze large amounts of unstructured digital data sets. Based on the differential evolution algorithm and semiclassical quantum simulations, we have recently proposed a method for classifying and analyzing the optical properties of organic pigments. In this paper, we present the results of modeling the absorption spectra of five carotenoids synthesized during the vital activity of the ascomycetous fungi: neurosporaxanthin, neurosporene, torulene, γ-carotene, and ζ-carotene. We calculated the absorption spectra for each pigment using the multimode Brownian oscillator theory, which allows us to evaluate the influence of molecular vibrations on the electronic transitions in the pigment. We applied a generalized spectral density function method to our modeling, taking into account the contributions of 13 vibrational modes with frequencies varying between 100 cm−1 and 3000 cm−1. This approach allowed us to gain a deeper understanding of how molecular vibrations affect the absorption spectra of these organic compounds. Thus, each absorption spectrum was associated with a unique set of Huang–Rhys factors (which represent the effective electron–phonon interaction). This set can be considered as a kind of “fingerprint” that characterizes the optical response of the pigment in the solvent.

Self-Trapped Excitons in 3R ZnIn2S4 with Broken Inversion Symmetry for High-Performance Photodetection.

Exploring novel materials with intrinsic self-trapped excitons (STEs) is crucial for advancing optoelectronic technologies. In this study, 2D 3R-phase ZnIn2S4, featuring broken inversion symmetry, is introduced to investigate intrinsic STEs. This material exhibits a broadband photoluminescence (PL) emission with a full width at half maximum of 164nm and a large Stokes shift of ≈0.6eV, which arises from the distortion of [ZnS4]6- tetrahedral unit induced by the symmetry breaking and strong electron-phonon coupling. The photophysical properties of the STEs exhibit a high Huang-Rhys factor (15.0), rapid STEs formation time (166fs), and extended STEs lifetime (1039ps), as demonstrated by experimental evidence from temperature-dependent PL, Raman spectroscopy, and ultrafast absorption spectroscopy. Additionally, STE-induced photoconductiveeffect is elucidated, indicating that intrinsic STEs in 3R-ZnIn2S4 can provide a synergistic effect that enhances absorption capacity, localization, and lifetime by capturing the self-trapped hole state. Consequently, the 2D 3R-ZnIn2S4 photodetector exhibits remarkable broad-spectrum photosensitivity, including a photo-switching ratio of 11286, response times of less than 0.6ms, responsivity of 15.2AW-1, detectivity of 1.02×10¹¹ Jones, and external quantum efficiency of 5032% under 375nm light. These findings provide new ideas for exploring materials with intrinsic STEs to achieve novel high-performance photodetector applications.

Multiple Resonance Quasi‐fluorescence from BN‐Doped Aromatic Compounds Modified with “Naphthalene” Units Approaches the BT.2020 Green Light Standard

AbstractDeveloping fluorophores that conform to the Broadcast Service Television 2020 (BT.2020) standard presents a formidable challenge. Here, we propose an innovative approach that integrates two and three‐boron/nitrogen (BN2)‐embedded [4]helicene subunits with naphthalene, resulting in the synthesis of two novel narrowband bright green quasi‐fluorescent emitters, NT‐2B and NT‐3B for ultra‐high‐definition displays. These emitters exhibit minimal reorganization energy and Huang–Rhys factor, emitting at 510 and 511 nm in dilute toluene solution with exceptionally narrow full width at half maximum values of 15 and 14 nm, respectively. Notably, NT‐2B demonstrates an impressive photoluminescence quantum yield of 92.5 %, rapid radiative decay rate, and slow non‐radiative decay rate. Owing to their narrowband emission characteristics and outstanding optoelectronic properties, corresponding OLEDs based on NT‐2B demonstrate a high external quantum efficiency of 30.6 %, with an FWHM value of 21.5 nm and a CIEy of 0.74, positioning it as one of the leading narrow‐band green emitters.

Multiple Resonance Quasi-fluorescence from BN-Doped Aromatic Compounds Modified with "Naphthalene" Units Approaches the BT.2020 Green Light Standard.

Developing fluorophores that conform to the Broadcast Service Television 2020 (BT.2020) standard presents a formidable challenge. Here, we propose an innovative approach that integrates two and three-boron/nitrogen (BN2)-embedded [4]helicene subunits with naphthalene, resulting in the synthesis of two novel narrowband bright green quasi-fluorescent emitters, NT-2B and NT-3B for ultra-high-definition displays. These emitters exhibit minimal reorganization energy and Huang-Rhys factor, emitting at 510 and 511 nm in dilute toluene solution with exceptionally narrow full width at half maximum values of 15 and 14 nm, respectively. Notably, NT-2B demonstrates an impressive photoluminescence quantum yield of 92.5 %, rapid radiative decay rate, and slow non-radiative decay rate. Owing to their narrowband emission characteristics and outstanding optoelectronic properties, corresponding OLEDs based on NT-2B demonstrate a high external quantum efficiency of 30.6 %, with an FWHM value of 21.5 nm and a CIEy of 0.74, positioning it as one of the leading narrow-band green emitters.

Abnormal Temperature Dependence of Huang-Rhys Factor and Exciton Recombination Kinetics in CsPbBr3 Perovskite Quantum Dots.

Anomalous thermal behaviors of excitonic luminescence in CsPbBr3 perovskite quantum dots (PQDs) were observed. It is found that the main luminescence peak originated from the excitonic radiative recombination assisted by the longitudinal-optical (LO) phonon, and its integrated intensity first declines as the temperature varies from 10 to 150 K and then turns to increase at ∼160 K, reaching a maximum value at 300 K. A model considering the thermal detrapping and transfer of electrons from a trap level is developed to interpret these abnormal thermal behaviors of the luminescence from the PQDs. On the other hand, the quantum-mechanical multimode Brownian oscillator model was employed to unravel that the Huang-Rhys factor exclusively characterizing the exciton-phonon coupling in the studied CsPbBr3 PQDs decreases from 1.65 at 10 K to 1.31 at 200 K.

Controlling Vibronic Coupling in Chlorophyll Proteins: The Effects of Excitonic Delocalization and Vibrational Localization.

Vibrational-electronic (vibronic) coupling plays a critical role in excitation energy transfer in molecular aggregates and pigment-protein complexes (PPCs). But the interplay between excitonic delocalization and vibronic interactions is complex, often leaving even qualitative questions as to what conceptual framework (e.g., Redfield versus Förster theory) should be used to interpret experimental results. To shed light on this issue, we report here on the interplay between excitonic delocalization and vibronic coupling in site-directed mutants of the water-soluble chlorophyll protein (WSCP), as reflected in 77 K fluorescence spectra. Experimentally, we find that in PPCs where excitonic delocalization is disrupted (either by mutagenesis or heterodimer formation), the relative intensity of the vibrational sideband (VSB) in fluorescence spectra is suppressed by up to 37% compared to that of the native protein. Numerical simulations reveal that this effect results from the localization of high-frequency vibrations in the coupled system; while excitonic delocalization suppresses the purely electronic transition due to H-aggregate-like dipole-dipole interference, high-frequency vibrations are unaffected, leading to a relative enhancement of the VSB. By comparing VSB intensities of PPCs both in the presence and absence of excitonic delocalization, we extract a set of "local" Huang-Rhys (HR) factors for Chl a in WSCP. More generally, our results suggest a significant role for geometric effects in controlling energy-transfer rates (which depend sensitively on absorption/fluorescence line shapes) in molecular aggregates and PPCs.

Mechanism of Pressure-Modulated Self-Trapped Exciton Emission in Cs2TeCl6 Double Perovskite.

Pressure-modulated self-trapped exciton (STE) emission mechanism in all-inorganic lead-free metal halide double perovskites characterized by large Stokes-shifted broadband emission, has attracted much attention across various fields such as optics, optoelectronics, and biomedical sciences. Here, by employing the all-inorganic lead-free metal halide double perovskite Cs2TeCl6 as a paradigm, the authors elucidate that the performance of STE emission can be modulated by pressure, attributable to the pressure-induced evolution of the electronic state (ES). Two ES transitions happen at pressures of 1.6 and 5.8GPa, sequentially. The electronic behaviors of Cs2TeCl6 can be jointly modulated by both pressure and ES transitions. When the pressure reaches 1.6GPa, the Huang-Rhys factor S, indicative of the strength of electron-phonon coupling, attains an optimum value of ≈12.0, correlating with the pressure-induced photoluminescence (PL) intensity of Cs2TeCl6 is 4.8-fold that of its PL intensity under ambient pressure. Through analyzing the pressure-dependent STE dynamic behavioral changes, the authors have revealed the microphysical mechanism underlying the pressure-modulated enhancement and quenching of STE emission in Cs2TeCl6.

(Invited) From PL-Inactive to PL-Active: Synthesis and Properties of Novel PL-Active 2D Lead-Free Double Perovskites Based on (PA)4AgInBr8

In this work, novel two-dimensional lead-free double perovskites ((R)4MaMbMcX8, a+b+c=2) were synthesized to achieve novel compositional and dimensional tunability. Specifically, manganese (Mn2+) is incorporated into (PA)4AgInBr8 (PA = CH3(CH2)2NH3+) to form (PA)4Ag1-0.5xMnxIn1-0.5xBr8 (0 ≤ x ≤ 1). These samples were tuned to be PL-emissive under room temperature via this manganese alloying strategy. Three emission pathways can be investigated: band edge emission, emission stemming from self-trapped excitons, and the energy transfer processes associated with Mn2+ center energy levels. Temperature-dependent PL elucidates two emissive modes: self-trapped exciton emission as well as Mn-center emission based on analysis of the associated Huang-Rhys factors. Overall, this work informs the development of additional light-emissive 2D lead-free double perovskites.

Frequency-Dependent Vibronic Effects in Steady State Energy Transport.

The interplay between electronic and intramolecular high-frequency vibrational degrees of freedom is ubiquitous in natural light-harvesting systems. Recent studies have indicated that an intramolecular vibrational donor-acceptor frequency difference can enhance energy transport. Here, we analyze the extent to which different intramolecular donor-acceptor vibrational frequencies affect excitation energy transport in the natural nonequilibrium steady state configuration. Comments are included on the less physical equilibrium case for comparison with the literature. It is found that for constant Huang-Rhys factors, whereas the acceptor population increases in the equilibrium case when the intramolecular vibrational frequency of the acceptor exceeds that of the donor, this increase is negligible for the nonequilibrium steady state. Therefore, these changes in acceptor population do not significantly enhance energy transport in the nonequilibrium steady state for the natural scenario of incoherent light excitation with biologically relevant parameters of typical photosynthetic complexes. Insight about a potential mechanism to optimize energy transfer in the nonequilibrium steady state based on increasing the harvesting time at the reaction center is analyzed.

Prediction of Shockley–Read–Hall lifetimes in strained layer superlattices for mid-wave and long-wave infrared photodetectors

We have calculated carrier nonradiative recombination lifetimes limited by Shockley–Read–Hall (SRH) centers in strained layer superlattices (SLSs) for mid-wave and long-wave infrared applications. The capture rate of an electron (hole) in the SLS's conduction (valence) band by the defect level is dominated by a multi-phonon process, which is orders-of-magnitude more efficient than the radiative process. Long-range polar coupling between electrons and optical phonons can account for the observed SRH lifetimes in a variety of SLSs reported in the literature. The capture rate depends on temperature rather weakly, consistent with experimental observations. The efficient capture is caused by the comparable electronic difference and lattice relaxation energy, Ect∼Sℏω, with S and ℏω being the Huang–Rhys factor and optical photon energy in the SLSs. A weaker polar coupling would give rise to a smaller capture cross section, which, for InAs/InAsSb SLSs, can be achieved by increasing Sb in the alloy region.

Extracting phonon coupling parameters from multi color center photoluminescence

Vibronic coupling of color centers plays a crucial role in their effectiveness for quantum technologies. This study presents a novel approach to extract key parameters, including the Huang–Rhys factor and the one-phonon coupling function, from photoluminescence spectra containing the signal from multiple color centers. Monotonic splines are used to represent the one-phonon coupling function, optimized using a variable-length non-dominated sorting genetic algorithm. Our method is applied to the combination of the well-studied negatively charged nitrogen-vacancy center and its less explored neutral counterpart in diamond, observed through photoluminescence at 14 K. Despite the complexity inherent in the theoretical framework governing phonon coupling in photoluminescence, we achieve robust fits, yielding a normalized root-mean-squared error of approximately 6%. The neutral nitrogen-vacancy center exhibits a Huang–Rhys factor of 3.0, while its negatively charged counterpart showcases a value of 3.95. The quasi-localized vibrations of both charge states are clearly present in the fitted one-phonon spectral function. Furthermore, the consistency of our methodology is bolstered by temperature-dependent photoluminescence, which was calculated up to numerical constants using fit-derived parameters, matching the experimental measurements up to 300 K.

Optical and EPR spectroscopy of manganese doped LiNaGe4O9 single crystals

The paper presents data on the study of optical absorption, photoluminescence and EPR of lithium-sodium tetragermanate crystals (LiNaGe4O9) doped with Mn ions. Optical spectra were measured in the range 11000–45000 cm−1 and temperatures 77–300 K. They are attributed to manganese in the +4 charge state. From the analysis of optical spectra, the crystal field strength Dq = 2175.2 cm−1 and Racah parameters A = 4065 cm−1, B = 813 cm−1, C = 3239 cm−1 were determined for the Mn4+ ions. The value of the Huang-Rhys factor SFHR = 17.56 indicates a strong electron-phonon interaction of the Mn4+ ion. The presence of Mn4+ ions was further confirmed by measurement of EPR spectra at microwave frequencies 8.9 and 320 GHz. EPR data show that Mn4+ ions occupy two structurally nonequivalent lattice sites with the formation of two Mn4+ centers: Mn1 and Mn2. From the angular dependences of the EPR spectra, the components of the g factor and the hyperfine interaction tensor A, the parameters of the axial D and rhombic E crystal field were determined for both centers. The axial constant D is large for both centers: 0.644 and 0.560 cm−1, respectively. Analysis of optical and EPR spectroscopic data testifies that Mn4+ ions replace the Ge4+ ions in oxygen octahedrons within the host. Structurally nonequivalent centers are attributed to manganese ions located in undistorted lattice sites (Mn1) and in sites perturbed by the LiNa antisite defect (Mn2).

Bismuth (Bi3+) and Tellurium (Te4+) doped Cs2ZrCl6 lead-free halide perovskite phosphors for white LEDs

Lead-free halide double-perovskite materials have been given extensive attention due to the charming fluorescent property and simple synthesis process. Their strong electro-acoustic coupling effects endow the materials with wideband emission properties and the tremendous potential application in white light emitting diodes (w-LEDs). Herein, the blue (456 nm) and yellow (578 nm) light emitting phosphors with broad band emission were synthesized by introducing the Bi3+ and Te4+ into the structure-stable and low toxicity Cs2ZrCl6 materials, respectively. The blue and yellow emission from 3P1 → 1S0 transitions of Bi3+ and Te4+ were achieved in Cs2ZrCl6: 7%Bi3+ and Cs2ZrCl6: 3%Te4+, where the large full width at half maximum (FWHM) values of 45 and 101 nm were attributed to the large Huang-Rhys factor and electro-acoustic coupling strength. The white LED fabricated through combining the 365 nm chip with the prepared blue and yellow phosphors exhibited wideband white light emission ranging from the 400–750 nm with correlated color temperature (CCT) 5028 K and good color rendering index (CRI) 84.

Isolated single-photon emitters with low Huang–Rhys factor in hexagonal boron nitride at room temperature

The development of stable room-temperature bright single-photon emitters using atomic defects in hexagonal boron nitride flakes (h-BN) provides significant promise for quantum technologies. However, an outstanding challenge in h-BN is the creation and detection of isolated, stable single-photon emitters with high emission rates and with very low Huang–Rhys (HR) factor. Here, we discuss the quantum photonic properties of a single, isolated, stable quantum emitter that emits single photons with a high emission rate and a low HR value of 0.6 ± 0.2 at room temperature. A scanning confocal image confirms the presence of a deserted, single-quantum emitter with a prominent zero-phonon line at ∼578 nm with a well-separated phonon sideband at 626 nm. The second-order intensity-intensity correlation measurement shows an anti-bunching dip of ∼0.25 with an emission lifetime of 2.46 ± 0.1 ns, reinforcing distinct features of the single-photon emitter. The importance of low-energy electron beam irradiation and subsequent annealing is emphasized to achieve stable, reproducible single-photon emitters.

Quantitative regulation of electron–phonon coupling

Electron–phonon (e–p) coupling plays a crucial role in various physical phenomena, and regulation of e–p coupling is vital for the exploration and design of high-performance materials. However, the current research on this topic lacks accurate quantification, hindering further understanding of the underlying physical processes and its applications. In this work, we demonstrate quantitative regulation of e–p coupling, by pressure engineering and in-situ spectroscopy. We successfully observe both a distinct vibrational mode and a strong Stokes shift in layered CrBr3, which are clear signatures of e–p coupling. This allows us to achieve precise quantification of the Huang–Rhys factor S at the actual sample temperature, thus accurately determining the e–p coupling strength. We further reveal that pressure efficiently regulates the e–p coupling in CrBr3, evidenced by a remarkable 40% increase in S value. Our results offer an approach for quantifying and modulating e–p coupling, which can be leveraged for exploring and designing functional materials with targeted e–p coupling strengths.

Computational study of K vacancy with an H interstitial defect in [formula omitted] crystal

The electronic structures, defect formations, defect transition levels and optical properties for VK+Hi defect models in KDP crystals have been studied based on DFT. Lattice dynamics methods give the most reasonable compensation mechanism for VK, namely compensation with the third-nearest Hi neighbor from VK for the paraelectric (PE) phase and compensation with the fourth-nearest neighbor Hi from VK for the ferroelectric (FE) phase. The defect formation energies indicate that the (VK+Hi)x (The superscript represents the charged state, the ‘x’ represents neutral, ‘’’ represents −1 charge state and ‘.’ represents +1 charge state.) is the main defect type in this kind of defect cluster and a self-trapped electron is located at Hi in the (VK + Hi)′ system. For (VK+Hi)x system, one electron is accommodated in VK. There is not a new defect state in the band gap. The Hi bonds with the O ion (0.99 Å) form a hydroxyl. For (VK + Hi)′ system, the hydroxyl is broken, the Hi exists in an atomic form and introduces new defect states in the band gap. As the large relaxation energy leads to a large Huang-Rhys factor, the Stokes red shifts will significantly affect the optical properties. A broad ultraviolet (UV) absorption band and emission band range from UV to visible are obtained originating from the defect cluster. We believe that the far-violet absorption peaks (167 nm and 179 nm) caused by defect cluster VK+Hi can significantly impact the optical damage threshold of the KDP.

Delocalizing Excitation for Highly‐Active Organic Photovoltaic Catalysts

AbstractLocalized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo‐induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron‐phonon coupling via rational fluoro‐substitution. The optimized 2FBP‐4F catalyst we develop here exhibits a minimized Huang–Rhys factor of 0.35 in solution, high dielectric constant and strong crystallization in the solid state. As a result, the energy barrier for exciton dissociation is decreased, and more importantly, polarons are unusually observed in 2FBP‐4F nanoparticles (NPs). With the increased hole transfer efficiency and prolonged charge carrier lifetime highly related to enhanced exciton delocalization, the PM6 : 2FBP‐4F heterojunction NPs at varied concentration exhibit much higher optimized photocatalytic activity (207.6–561.8 mmol h−1 g−1) for hydrogen evolution than the control PM6 : BP‐4F and PM6 : 2FBP‐6F NPs, as well as other reported photocatalysts under simulated solar light (AM 1.5G, 100 mW cm−2).

Delocalizing Excitation for Highly-Active Organic Photovoltaic Catalysts.

Localized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo-induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron-phonon coupling via rational fluoro-substitution. The optimized 2FBP-4F catalyst we develop here exhibits a minimized Huang-Rhys factor of 0.35 in solution, high dielectric constant and strong crystallization in the solid state. As a result, the energy barrier for exciton dissociation is decreased, and more importantly, polarons are unusually observed in 2FBP-4F nanoparticles (NPs). With the increased hole transfer efficiency and prolonged charge carrier lifetime highly related to enhanced exciton delocalization, the PM6 : 2FBP-4F heterojunction NPs at varied concentration exhibit much higher optimized photocatalytic activity (207.6-561.8 mmol h-1 g-1) for hydrogen evolution than the control PM6 : BP-4F and PM6 : 2FBP-6F NPs, as well as other reported photocatalysts under simulated solar light (AM 1.5G, 100 mW cm-2).

Ultrafast Dynamics of Self-Trapped Excitons in Cs2AgInCl6:Al3+ Double Perovskite Nanocrystals.

It is a huge challenge to increase the photoluminescence (PL) of lead-free halide perovskites, and understanding the mechanism behind exciton dynamics can provide a valuable solution. Herein, we achieved enhanced broad-band emission at ambient conditions in Cs2AgInCl6 by tuning self-trapped excitons (STEs) through Al3+ doping. Cryogenic measurements showed an inhomogeneous nature of STE emission due to the presence of defect states and is subject to thermal quenching. An increased Huang-Rhys factor (S-factor) resulted in better electron-phonon coupling and high-density STE states post Al3+ doping. Femtosecond transient absorption (fs-TA) results provided insights into the distribution dynamics of excitons, which occurs through gradient energy levels from free excitons (FE) to STEs, where each STE state potentially possesses higher quantized energy states. Overall, this study aims to comprehend the origins of self-trapping and decay of STEs in Cs2AgInCl6:Al3+ and emphasizes the potential of compositional engineering to mitigate self-trapping in this material.

Pressure-induced emission in 0D metal halide (EATMP)SbBr5 by regulating exciton-phonon coupling

Zero-dimensional (0D) hybrid metal halides are considered as promising light-emitting materials due to their unique broadband emission from self-trapped excitons (STEs). Despite substantial progress in the development of these materials, the photoluminescence quantum yields (PLQY) of hybrid Sb–Br analogs have not fully realized the capabilities of these materials, necessitating a better fundamental understanding of the structure-property relationship. Here, we have achieved a pressure-induced emission in 0D (EATMP)SbBr5 (EATMP = (2-aminoethyl)trimethylphosphanium) and the underlying mechanisms are investigated using in situ experimental characterization and first-principles calculations. The pressure-induced reduction in the overlap between the STE states and ground states (GSs) results in the suppression of phonon-assisted non-radiative decay. The photoluminescence (PL) evolution is systematically demonstrated to be controlled by the pressure-regulated exciton-phonon coupling, which can be quantified using Huang-Rhys factor S. Through detailed studies of the S-PLQY relation in a series of 0D hybrid antimony halides, we establish a quantitative structure-property relationship that regulating S value toward 21 leads to the optimized emission. This work not only sheds light on pressure-induced emission in 0D hybrid metal halides but also provides valuable insights into the design principles for enhancing the PLQY in this class of materials.