Decay Rate Of Excited State Research Articles

Dicyanomethylenated Diaryldihydropentalenediones that Vary Excited State Decay Rates without Changing Emission Wavelengths

Abstract2‐(3,6‐Bis(4‐methoxyphenyl)‐2,2,5,5‐tetramethyl‐4‐oxo‐4,5‐dihydropentalen‐1(2H)‐ylidene)malononitrile (DPM‐An) and 2,2′‐(3,6‐bis(4‐methoxyphenyl)‐2,2,5,5‐tetramethyl‐2,5‐dihydropentalene‐1,4‐diylidene)dimalononitrile (DPD‐An), both bearing the 2,5‐dihydropentalene core and intramolecular electron donor–acceptor moieties, were prepared and subjected to photophysical studies. The absorption spectra of DPM‐An and DPD‐An in CH2Cl2 at room temperature contain maxima at similar wavelengths of 406 and 409 nm, respectively. These substances do not luminesce in CH2Cl2 solution at room temperature, but they do emit light when present in poly(methyl methacrylate) films. Interestingly, DPM‐An and DPD‐An in the film forms display nearly identical emission (EM) spectra with respective maxima at 592 and 594 nm. In contrast, DPD‐An has a longer EM lifetime than does DPM‐An. Therefore, the dihydropentalene derivatives, exemplified by DPM‐An and DPD‐An, may be a family of substances in which excited state decay rate can be varied without changing EM wavelengths.

Effect of electron–phonon interactions on a three-level QD-based spaser: linear and quadratic potentials

Abstract In this article, we study the effect of electron–phonon interaction on a spaser (surface plasmon amplification by stimulated emission of radiation) system consisting of a metal nanoparticle surrounded by a large number of quantum dots (QDs). Usually, the effect of electron–phonon interaction is neglected in the spaser-related literature. However, gain media, in this case QDs, attributed by the large Raman scattering cross-section, exhibit stronger electron–phonon interaction. In the present work, we investigate the effects of electron–phonon interaction on a three-level QD-based spaser. We consider two types of interaction potentials, linear and quadratic, and analyse their effects individually. First, we focus on the linear electron–phonon interaction that perturbs the electrons present in the excited state. This yields a periodic steady-state number of localized surface plasmons (LSPs). The accompanying analytic solution reveals that the population inversion of the gain medium depends on the linear potential strength (Frohlich constant) but does not affect the threshold of spaser considerably for the given numerical parameters. In addition to the LSP, phonons are generated during this process, the temporal dynamics of which are also presented here. Initially, the number of phonons exhibit decaying periodic oscillations, whose amplitude depends on the strength of the electron–phonon interaction. Under continuous pumping, at later times, the number of phonons reaches a steady-state value, which may find potential applications in the realization of continuous phonon nanolasers. Furthermore, the effect of the quadratic potential is investigated phenomenologically by increasing the excited-state decay rate. This results in numerous LSPs and an intense spaser spectrum.

First-Principles Calculations of Excited-State Decay Rate Constants in Organic Fluorophores.

In this Perspective, we discuss recent advances made to evaluate from first-principles the excited-state decay rate constants of organic fluorophores, focusing on the so-called static strategy. In this strategy, one essentially takes advantage of Fermi's golden rule (FGR) to evaluate rate constants at key points of the potential energy surfaces, a procedure that can be refined in a variety of ways. In this way, the radiative rate constant can be straightforwardly obtained by integrating the fluorescence line shape, itself determined from vibronic calculations. Likewise, FGR allows for a consistent calculation of the internal conversion (related to the non-adiabatic couplings) in the weak-coupling regime and intersystem crossing rates, therefore giving access to estimates of the emission yields when no complex photophysical phenomenon is at play. Beyond outlining the underlying theories, we summarize here the results of benchmarks performed for various types of rates, highlighting that both the quality of the vibronic calculations and the accuracy of the relative energies are crucial to reaching semiquantitative estimates. Finally, we illustrate the successes and challenges in determining the fluorescence quantum yields using a series of organic fluorophores.

Influence of Mode-Specific Excitation on the Nonadiabatic Dynamics of Methyl Nitrate (CH3ONO2).

The impact of mode-specific vibrational excitations on initial-preparation conditions was studied by examining the excited-state population decay rates in the nonadiabatic dynamics of methyl nitrate (CH3ONO2). In particular, exciting a few specific modes by adding a single quantum of energy clearly decelerated the nonadiabatic dynamics population decay rates. The underlying reason for this slower population decay was explained by analyzing the profiles of the excited-state potential energy surfaces in the Franck-Condon regions and the topology of the S1/S0 conical intersection. This study not only provides physical insights into the key mechanisms controlling nonadiabatic dynamics but also shows the possibility of controlling nonadiabatic dynamics via mode-specific vibrational excitations.

Tunable resonance Raman scattering of quantum dots in a nonlinear excitation regime.

Controllable tuning of electron-phonon coupling strength and excited state dynamics is important for the understanding of resonance Raman scattering in low-dimensional semiconductors. Here, we report a significant and reversible field-induced modulation in absolute resonance Raman intensity of quantum dots using ionic liquid gating. Meanwhile, a potential-dependent nonlinear relationship is present between Raman intensity and excitation power density. By exploring the parameter space within a time domain model, we find that the Raman intensity variation is mainly determined by the homogeneous linewidth. We further propose that the Fermi level positions and exciton species play key roles in the excited state decay rates.

Tailoring D-π-A architectures with hybridized local and charge transfer fluorophores exhibiting high electroluminescence exciton utilization and low threshold amplified spontaneous emission.

Novel amorphous compounds which could simultaneously use 25% singlet excitons and 75% triplet excitons as the energy source for light amplification enable the reduction of the threshold current density for electrically pumped organic semiconductor laser diodes (OSLDs); however, there is always a trade-off between the high radiative decay rate of the local excited (LE) state that is required for amplified spontaneous emission (ASE) and high exciton utilization benefiting from the charge-transfer (CT) state during electroluminescence (EL). Herein, we have explored a delicate balance to achieve both low ASE threshold and high EL exciton utilization by adopting a carefully tailored hybridized local and charge-transfer (HLCT) molecular design. A series of donor-π-acceptor (D-π-A) molecules (SBz-1, SBz-2 and SBz-3) are synthesized, and the structural change mainly refers to the spatial distance between D and A which could regulate the excited-state character via adjusting the CT length. Notably, the ASE phenomenon with a low threshold (2.97 μJ cm-2) and a high exciton utilization of 57.6% are achieved at the same time for SBz-2 with an appropriate CT length. The results provide guidance for molecular design toward harvesting triplet excitons in organic laser materials.

Quantitative prediction of excited-state decay rates for radical anion photocatalysts.

We present a computational approach for predicting key properties of organic radical anions, including excited-state lifetimes and redox potentials. The approach shows good agreement with experimental data and has potential for in silico screening to facilitate the rational design of photocatalysts.

Computational studies on the excited state decay rates in aggregates of two‐coordinate Cu (I) complexes: Thermally Activated Delayed Fluorescence and Aggregation Induced Emis

AbstractTwo‐coordinate Cu (I) complexes have attracted great interest recently because of the rich photophysical property in solid state, including the aggregation‐induced thermal activated delayed fluorescence. Here, we summarize our theoretical investigations on the excited state structure and decay dynamics for the two‐coordinate Cu (I) complexes in solution phase and solid state by the thermal vibration correlation function rate formalism we developed earlier coupled with time‐dependent density‐functional theory within polarizable continuum model and hybrid quantum and molecular mechanics. First, for the CAACCu (I)Cl complex, we found that the nature of the excited state undergoes a change from metal‐to‐ligand charge transfer (MLCT) in solution to hybrid halogen‐to‐ligand charge transfer and MLCT in solid state. The bending vibrations of the CCuCl and CuCN bonds are restricted in aggregates, reducing the non‐radiative decay rate to cause strong solid‐state fluorescence. Second, for CAACCu (I)Cz, we found that both intersystem crossing (ISC) and reverse intersystem crossing (rISC) are enhanced by 2–4 orders of magnitudes upon aggregation, leading to highly efficient thermally activated delayed fluorescence (TADF). The enhanced ISC and rISC rates can be attributed to the increase of the metal proportion in the frontier molecular orbitals, leading to an enhanced spin−orbit coupling between S1 and T1. The reaction barriers for ISC and rISC are much lower in solution than that in aggregate phase resulting in a decrease in energy gap and an increase in the relative reorganization energy through bending the angle ∠C − Cu − N for T1. Our theoretical studies provide a clear rationalization for the highly efficient solid‐state luminescence character of two‐coordinate Cu (I) complexes and may clarify the ongoing dispute on the understanding of the high TADF quantum efficiency.

Anti-Kasha Fluorescence in Molecular Entities: Central Role of Electron-Vibrational Coupling.

According to Kasha's rule, the emission of a photon in a molecular system always comes from the lowest excited state. A corollary of this rule (i.e., the Kasha-Vavilov rule) states that the emission spectra are independent of the excitation wavelength. Although these rules apply for most of the molecular systems, violations of these rules are often reported. The prototypical case of a Kasha's rule violation is the fluorescence observed from S2 in azulene. Thanks to the advances in both theoretical and experimental research, other types of anomalous fluorescence (e.g., excitation energy transfer (EET)-based dual emissions, thermally activated fluorescence, etc.) are more recurrently reported in the literature. Sometimes, these anomalous processes involve higher-lying excited states but are mechanistically different from the azulene-like anomalous fluorescence. However, the underlying mechanisms leading to these anomalous emissions can be numerous and are not yet well understood.In order to shed some light on the above phenomena, this Account provides a comprehensive review of this topic. We herein report quantum chemical investigations in target molecular systems breaking Kasha's rule. The latter molecules were chosen because they were unambiguously reported to display anti-Kasha fluorescence. Our studies highlight three different types of anti-Kasha scenarios. Specifically, (i) the strong electronic, weak vibrational nonadiabatic coupling (NAC) regime (here named the type I case, i.e., azulene-like); (ii) the strong electronic, strong vibrational NAC regime (type II case, i.e., thermally activated S2 fluorescence); and the (iii) very weak electronic NAC regime (type III case, i.e., EET dyads). In addition, by combining state-of-the-art quantum chemical calculations with excited-state decay rate theories and appropriate excited-state kinetic models, we provide semiquantitative estimations of photoluminescence quantum yields for the most rigid molecular entities. Finally, we propose the use of simple theoretical descriptors relying on calculations of the excited-state density difference and the electron-vibrational coupling to classify anomalous emissions according to their coupling scenario.Besides the fundamental interest of the above investigations, the herein developed computational protocols and descriptors will be useful for the tailored design of dyes with tunable and unconventional fluorescence properties and their exploitation in a wide range of areas (i.e., from organic light-emitting diodes (OLEDs) to bioimaging, small-molecule fluorescent probes, and photocatalysis). Finally, our theoretical framework enables the attainment of a holistic understanding of the interconversion processes between excited states, where the electron-vibrational coupling is shown to play a central role in determining the efficacy.

Fluorescent molecular rotor probes nanosecond viscosity changes.

Viscosity is a key property of liquids, but it is difficult to measure in short-lived, metastable samples due to the long measuring times required by conventional rheology. Here, we show how this problem can be solved by using fluorescent molecular rotors. The excited-state fluorescence decay rate of these molecules is sensitive to the viscosity of their local environment, and by combining pulsed laser excitation with time-resolved fluorescence detection, we can measure viscosities with a time resolution of a few ns. We demonstrate this by measuring in real time the viscosity change in glycerol induced by a nanosecond temperature jump. This new approach makes it possible to measure the viscosity of extremely short-lived states of matter.

Disentangling Pauli Blocking of Atomic Decay from Cooperative Radiation and Atomic Motion in a 2D Fermi Gas.

The observation of Pauli blocking of atomic spontaneous decay via direct measurements of the atomic population requires the use of long-lived atomic gases where quantum statistics, atom recoil, and cooperative radiative processes are all relevant. We develop a theoretical framework capable of simultaneously accounting for all these effects in the many-body quantum degenerate regime. We apply it to atoms in a single 2D pancake or arrays of pancakes featuring an effective Λ level structure (one excited and two degenerate ground states). We identify a parameter window in which a factor of 2 extension in the atomic lifetime clearly attributable to Pauli blocking should be experimentally observable in deeply degenerate gases with ∼10^{3} atoms. We experimentally observe a suppressed excited-state decay rate, fully consistent with the theory prediction of an enhanced excited-state lifetime, on the ^{1}S_{0}-^{3}P_{1} transition in ^{87}Sr atoms.

TiO2–rGO nanocomposites with high rGO content and luminescence quenching through green redox synthesis

We developed TiO2–rGO nanocomposites with high exfoliated rGO content upto 47.1% (TG4) by weight hitherto not reported, through green redox synthesis. Progressive reduction of TiO2 nanocrystal size and their in situ intercalation occurred on increasing rGO via one pot synthesis, not reported previously and forming highly stable Ti–O–C bonds. With increase in rGO content, the exfoliation in the nanocomposite was also limited to single-few layered graphene oxide sheets through use of ascorbic acid avoiding restacking, and thereby the recombination of photogenerated carriers. TG4 showed 50% photoluminescence (PL) quenching indicating long-lived electron transfer state with rGO and apparent rate of nonradiative excited state decay of 1.15 × 108 s−1. Details of lattice orientation, Raman spectra, electronic states and PL lifetime decay are discussed to elucidate effective charge carrier separation in the nanocomposite. Near complete photodegradation of Alizarin Yellow GG azo dye, an industrial pollutant, could be obtained under direct sunlight using TG4 as catalyst.

Unravelling the ultrafast dynamics of a N-BODIPY compound

Although the photophysics of BODIPY compounds has been widely investigated in the last few years, their analogues N-BODIPY, with nitrogen substitution at the boron center, did not receive comparable attention. In this work we report the synthesis and photochemical characterization of a substituted N-BODIPY compound, by means of a combined theoretical and spectroscopic approach. Compared to a standard BODIPY, the compound under investigation presents a lower fluorescence quantum yield (QY) in the visible region. The excited state relaxation dynamics of the dye was studied in different solvents, showing further fluorescence quenching in polar solvents, and excited state decay rates strongly dependent on the environment polarity. The role of the pendant moieties and the involvement of charge transfer states in the excited state dynamics was experimentally addressed by transient absorption spectroscopy, and further analyzed with TD-DFT calculations, which allowed precise assignment of the transient signals to the correspondent electronic configuration. The complete picture of the N-BODIPY behavior shows the presence of both charge transfer and localized states, influencing the observed photophysics to different amounts, depending on the excitation conditions and the surrounding environment.

Aggregation-Enhanced Thermally Activated Delayed Fluorescence Efficiency for Two-Coordinate Carbene-Metal-Amide Complexes: A QM/MM Study.

The two-coordinate carbene-metal-amide complexes have attracted a great deal of attention due to their remarkable thermally activated delayed fluorescence (TADF) properties, giving them promise in organic light-emitting diode application. To reveal the inherent mechanism, we take CAAC-Cu(I)-Cz and CAAC-Au(I)-Cz as examples to investigate the photophysical properties in solution and solid phases by combining quantum mechanics/molecular mechanics approaches for the electronic structure and the thermal vibration correlation function formalism for the excited-state decay rates. We found that both intersystem crossing (ISC) and its reverse (rISC) are enhanced by 2-4 orders of magnitude upon aggregation, leading to highly efficient TADF, because (i) the metal proportion in the frontier molecular orbitals increases, leading to an enhanced spin-orbit coupling strength between S1 and T1, and (ii) the reaction barriers for ISC and rISC are much lower in solution than in aggregate phases through a decrease in energy gap ΔEST and an increase in the relative reorganization energy through bending the angle ∠C2-Cu-N1 for T1. We propose a pump-probe time-resolved infrared spectroscopy study to verify the mechanism. These findings can clarify the ongoing dispute over the understanding of the high TADF quantum efficiency for two-coordinate metal complexes.

Face-to-Face Orientation of Quasiplanar Donor and Acceptor Enables Highly Efficient Intramolecular Exciplex Fluorescence.

Intramolecular through-space charge-transfer (TSCT) excited states have been exploited for developing thermally activated delayed fluorescence (TADF) emitters, but the tuning of excited state dynamics by conformational engineering remains sparse. Designed here is a series of TSCT emitters with precisely controlled alignment of the donor and acceptor segments. With increasing intramolecular π-π interactions, the radiative decay rate of the lowest singlet excited state (S1 ) progressively increased together with a suppression of nonradiative decay, leading to significantly enhanced photoluminescence quantum yields of up to 0.99 in doped thin films. A high-efficiency electroluminescence device, with a maximum external quantum efficiency (EQE) of 23.96 %, was achieved and maintains >20 % at a brightness of 1000 cd m-2 . This work sheds light on the importance of conformation control for achieving high-efficiency intramolecular exciplex emitters.

Face‐to‐Face Orientation of Quasiplanar Donor and Acceptor Enables Highly Efficient Intramolecular Exciplex Fluorescence

AbstractIntramolecular through‐space charge‐transfer (TSCT) excited states have been exploited for developing thermally activated delayed fluorescence (TADF) emitters, but the tuning of excited state dynamics by conformational engineering remains sparse. Designed here is a series of TSCT emitters with precisely controlled alignment of the donor and acceptor segments. With increasing intramolecular π–π interactions, the radiative decay rate of the lowest singlet excited state (S1) progressively increased together with a suppression of nonradiative decay, leading to significantly enhanced photoluminescence quantum yields of up to 0.99 in doped thin films. A high‐efficiency electroluminescence device, with a maximum external quantum efficiency (EQE) of 23.96 %, was achieved and maintains >20 % at a brightness of 1000 cd m−2. This work sheds light on the importance of conformation control for achieving high‐efficiency intramolecular exciplex emitters.

Node-Dependent Photoinduced Electron Transfer in Third-Generation 2D MOFs Containing Earth-Abundant Metal Ions.

Five isostructural 2D metal-organic frameworks (MOFs), based on a photoactive CuI metallolinker and mixed mono-/dinuclear secondary building units (SBUs), are reported. The MOFs 1(M) (M = Mn, Co, Cu, Zn, and Cd) exhibit broad absorption across the visible-light spectrum and emission centered at ca. 730 nm. Upon photoexcitation, the rigidity of the framework hinders the pseudo-Jahn-Teller distortion of the metallolinker's excited state, providing efficient intersystem crossing into the triplet state. Rapid luminescence quenching in 1(Cu) and 1(Co) suggests photoinduced electron transfer (PET) to the SBUs, whereas lifetimes of up to 22.2 ns are observed in 1(Zn). The quantum yields relative to the parent photosensitizer (PS) decrease for metal nodes containing transition metal ions with partially occupied d-orbitals but increase for the d10 systems CdII and ZnII by a factor of up to 6. Importantly, the excited state decay rates directly correlate with the occupancy of the [MII(OH2)]x moieties in the MOFs providing nonradiative decay pathways via O-H oscillators. Cyclovoltammetry reveals minor changes in CuI/II oxidation potential, with excited-state reduction potentials for 1(M) rivalling Ru analogues. These results establish bis(diimine)copper(I) photosensitizers as viable metallolinkers for MOFs and present a rare example of an isostructural series obtained from a photosensitive metallolinker.

Speeding up particle slowing using shortcuts to adiabaticity

We propose a method for slowing particles by laser fields that potentially has the ability to generate large forces without the associated momentum diffusion that results from the random directions of spontaneously scattered photons. In this method, time-resolved laser pulses with periodically modified detunings address an ultranarrow electronic transition to reduce the particle momentum through repeated absorption and stimulated emission cycles. We implement a shortcut to adiabaticity approach that is based on Lewis-Riesenfeld invariant theory. This affords our scheme the advantages of adiabatic transfer, where there can be an intrinsic insensitivity to the precise strength and detuning characteristics of the applied field, with the advantages of rapid transfer that is necessary for obtaining a short slowing distance. For typical parameters of a thermal oven source that generates a particle beam with a central velocity on the order of meters per second, this could result in slowing the particles to near stationary in less than a millimeter. We compare the slowing scheme to widely-implemented slowing techniques that rely on radiation pressure forces and show the advantages that potentially arise when the excited state decay rate is small. Thus, this scheme is a particularly promising candidate to slow narrow-linewidth systems that lack closed cycling transitions, such as occurs in certain molecules.

Thermal Vibration Correlation Function Formalism for Molecular Excited State Decay Rates

Thermal Vibration Correlation Function Formalism for Molecular Excited State Decay Rates

Computational Protocol To Predict Anti-Kasha Emissions: The Case of Azulene Derivatives.

In this contribution, we present a computational protocol to predict anti-Kasha photoluminescence. The herein developed protocol is based on state-of-the-art quantum chemical calculations and excited-state decay rate theories (i.e., thermal vibration correlation function formalism), along with appropriate kinetic models which include all relevant electronic states. This protocol is validated for a series of azulene derivatives. For this series, we have computed absorption and emission spectra for both their first and second excited states, their radiative and nonradiative rates, as well as fluorescence yields from the two different excited states. All the studied azulene derivatives are predicted to exclusively display anomalous anti-Kasha S2 emission. A quantitative agreement for the herein computed excited-state spectra, lifetimes, and fluorescence quantum yields is obtained with respect to the experimental values. Given the increasing interest in anti-Kasha emitters, we foresee that the herein developed computational protocol can be used to prescreen dyes with the desired aforementioned anomalous photoluminescence properties.