Population Of Excited States Research Articles

Temperature‐Driven Axial‐Equatorial Isomerism and Magnetic Relaxation on Low‐Spin Co(II) Borohydride Complexes

Comprehensive SummaryCrystalline materials with diastereomerism serve as ideal prototypes for investigating the influence of coordination environments on chemophysical properties. In this study, we synthesized a pair of axial‐equatorial isomers [Co(II)(HB(timtBu)3)(cis‐dppen)](BF4)·solv ([HB(timtBu)3]− = hydrotris(3‐tertbutyl‐2‐thioxoimidazol‐1‐yl)borate; cis‐dppen = cis‐1,2‐bis(diphenylphosphino)ethene; solv = 0.5THF·2H2O and 2H2O for ax‐CoHS2P2 and eq‐CoHS2P2, respectively), by varying the crystallization temperatures. Despite both diastereoisomers adopting distorted square pyramidal geometries, the bidentate cis‐dppen ligand chelates to the central Co(II) either in an axial‐equatorial or equatorial‐equatorial manner, with a boron‐hydrogen binding to the metal center. Magnetic studies reveal differences in g‐values between these axial‐equatorial isomers. X‐band electron paramagnetic resonance spectra suggest rapid equilibrium and potential conformational interconversion in response to temperature changes in solution. Magnetic measurements indicate field‐induced slow relaxation of magnetization in this low‐spin S = 1/2 system, with spin‐lattice relaxations dominated by Raman and quantum tunneling of magnetization mechanisms due to the absence of thermally populated excited states.

Kinetic Basis for the Design of Azobenzene-Based Photoswitchable A2a Adenosine Receptor Ligands.

Photoisomerization of ligands is a key process in the field of photopharmacology. Thus, the kinetics and efficiency of this initial photoreaction are of great importance but can be influenced by the molecular environment of the binding pocket and the resulting confinement of the reaction pathway. In this study, we investigated the photoisomerization of an azobenzene derivative of the anti-Parkinson's drug istradefylline. To identify the impact of the binding pocket, the ligand was examined in solution and bound to its target protein, the A2a adenosine receptor (A2aR), belonging to the family of G protein-coupled receptors (GPCRs). Although the overall efficiency of isomerization is reduced when the ligand is bound, the initial photoreaction experiences little influence from the binding pocket. However, protein-coupled motion promotes a longer-lived excited-state population and thus leads to a reduction in efficiency. The results provide the kinetic basis for a photoswitchable GPCR ligand and demonstrate the influence of the binding pocket on fundamental photochemistry.

Temperature Controlled Decay and Pendulum Dynamics of Green Fluorescent Protein (GFP) Chromophore.

The excited-state dynamics of the GFP chromophore, HBDI- (anionic p-hydroxybenzylidene-2,3-dimethylimidazolinone), were investigated through a combination of theoretical nonadiabatic molecular dynamics (NAMD) simulations and femtosecond transient absorption spectroscopy (fs-TA). The NAMD simulations revealed that the primary dynamics in excited states involve the formation of a P-twisted intermediate (S1min,P), which undergoes pendulum-like oscillations with respect to ϕ = 90°. This motion serves as a reservoir for the excited-state population and the primary source of fluorescence. Rather than a direct channel from the major S1min,P, a coordinated pathway of S1min,P → S1min → S1min,I → S0 is responsible for the decay to the ground state, emphasizing the importance of planar intermediate (S1min) formation. The experimental fs-TA spectra confirmed these dynamics, revealing three distinct time scales (340-470 fs, 1.4 ps, and 8.3 ps), corresponding to the formation of S1min,P and its decay governed by the coordinated pathway. At low temperatures, the coordinated decay pathway is suppressed, leading to prolonged fluorescence lifetimes, consistent with low-temperature experimental results. This study presents a new model for the excited-state dynamics of GFP chromophore, suggesting that pendulum motion and the coordinated decay pathway play a crucial role in regulating fluorescence intensity.

1,4-Benzodioxane Substituted Aza-BODIPY: Towards Photostable yet Efficient Triplet Photosensitizer.

We report herein the synthesis of aza-BODIPY substituted with 1,4-benzodioxane-6-yl substituents at 3,5 positions of the chromophore system. Both pyrrole rings of the aza-BODIPY in question were substituted with bromine atoms in order to induce highly desirable photophysical properties, such as highly populated excited triplet state (T1) and long excited triplet-state lifetime (τT) of 21 μs. The photosensitized oxygenation of a model compounds, viz. DPBF, points to a high singlet oxygen and/or other ROS formation quantum yield of 0.42. The photosensitizer studied exhibited an absorption band within the so-called "therapeutic window", with λabs 678 nm. As estimated by CV/DPV measurements the 1,4-benzodioxane-6-yl substituted aza-BODIPYs studied exhibited a multi-electron oxidations at a relatively low potentials (Eox), pointing to the very good electron-donating properties of these molecules. High photostability and thermal stability was observed for all compounds studied. The good singlet oxygen quantum yield measured combined with an exceptional photostability makes this aza-BODIPY a promising candidate for applications such as photocatalysis and photodynamic therapy (PDT).

Computational Assessment of Novel Ruthenium Phenoxazine‐Based Complexes as Photosensitizers in Photodynamic Therapy

AbstractA computational examination of two new polypyridyl ruthenium complexes, containing meldola blue (MDB) and nile blue (NB) chromophores, is here reported in order to assess the applicability of phenoxazine‐containing complexes in photodynamic therapy (PDT). The designed complexes, named Ru‐3ENB and Ru‐3EMDB, are based on a recently synthesized Ru(II)‐based complex bearing a bipyridyl‐ethynyl‐Nile Red (NR) ligand and proposed for PDT applications. DFT outcomes elucidated how the replacement of NR with MDB induces a red shift of the maximum absorption wavelength within the therapeutic window, up to 638 nm. A change in the molecular orbitals involved in the population of excited states was observed upon chromophore substitution that results in ISC kinetic significantly faster than that computed for the synthesized complex Ru‐3ENR.

Sensitivity Analysis of Excited-State Population in Plasma Based on Relative Entropy.

A highly versatile evaluation method is proposed for transient plasmas based on statistical physics. It would be beneficial in various industrial sectors, including semiconductors and automobiles. Our research focused on low-energy plasmas in laboratory settings, and they were assessed via our proposed method, which incorporates relative entropy and fractional Brownian motion, based on a revised collisional-radiative model. By introducing an indicator to evaluate how far a system is from its steady state, both the trend of entropy and the radiative process' contribution to the lifetime of excited states were considered. The high statistical weight of some excited states may act as a bottleneck in the plasma's energy relaxation throughout the system to a steady state. By deepening our understanding of how energy flows through plasmas, we anticipate potential contributions to resolving global environmental issues and fostering technological innovation in plasma-related industrial fields.

A second-order kinetic model for global analysis of vibrational polariton dynamics.

The interaction between cavity photons and molecular vibrations leads to the formation of vibrational polaritons, which have demonstrated the ability to influence chemical reactivity and change material characteristics. Although ultrafast spectroscopy has been extensively applied to study vibrational polaritons, the nonlinear relationship between signal and quantum state population complicates the analysis of their kinetics. Here, we employ a second-order kinetic model and transform matrix method (TMM) to develop an effective model to capture the nonlinear relationship between the two-dimensional IR (or pump-probe) signal and excited state populations. We test this method on two types of kinetics: a sequential relaxation from the second to the first excited states of dark modes, and a Raman state relaxing into the first excited state. By globally fitting the simulated data, we demonstrate accurate extraction of relaxation rates and the ability to identify intermediate species by comparing the species spectra with theoretical ground truth, validating our method. This study demonstrates the efficacy of a second-order TMM approximation in capturing essential spectral features with up to 10% excited state population, simplifying global analysis and enabling straightforward extraction of kinetic parameters, thus empowering our methodology in understanding excited-state dynamics in polariton systems.

New theoretical insights on the nonradiative relaxation mechanism of the core structure of mycosporines: The amino-cyclohexenone central template.

We present a comprehensive computational study describing the excited state dynamics and consequent photostability of amino-cyclohexenone (ACyO), the central template of mycosporine systems, widely recognized for their photoprotection of aquatic species. Photoexcitation to the first excited electronic state (S1, 1nπ*) of ACyO is considered an optically dark transition, while photoexcitation to the second excited electronic state (S21ππ*) is an optically bright 1ππ* transition and largely responsible for UV absorption properties of this molecule. We show that following initial photoexcitation to S2, ACyO relaxes via two competing deactivation mechanisms, each mediated by an S1/S0 conical intersection, which directs the excited state population to the electronic ground state (S0). Our abinitio computational results are supported with nonadiabatic dynamics simulation results, yielding an excited state lifetime of ∼280fs for this system in vacuo. These results explain the inherent photostability of this core structure, commonplace in a wide range of microorganisms.

Unveiling the Mechanism of Plasmon Photocatalysis via Multiquantum Vibrational Excitation.

Plasmon photocatalysis reactions are thought to occur through vibrationally activated reactants, driven by nonthermal energy transfer from plasmon-induced hot carriers. However, a detailed quantum-state-level understanding and quantification of the activation have been lacking. Using anti-Stokes surface-enhanced Raman scattering (SERS) spectroscopy, we mapped the vibrational population distributions of reactants on plasmon-excited nanostructures. Our results reveal a highly nonthermal distribution with an anomalously enhanced population of multiquantum excited states (v ≥ 2). The shape of the distribution and its dependence on local field intensity and excitation wavelength cannot be explained by photothermal heating or vibronic optical transitions of the metal-molecule complex. Instead, it can be modeled by hot electron-molecule energy transfer mediated by the transient negative ions, establishing direct links among nonthermal reactant activation, plasmon-induced hot electrons, and negative ion resonances. Moreover, the presence of multiquantum excited reactants, which are far more reactive than those in the ground state or first excited state, presents opportunities for vibrationally controlling chemical selectivities.

Chiral Perovskite Heterostructure Films of CsPbBr3 Quantum Dots and 2D Chiral Perovskite with Circularly Polarized Luminescence Performance and Energy Transfer.

This work reports the synthesis of chiral perovskite heterostructure films by combining a two-dimensional (2D) chiral (R-/S-MBA)2PbI4 perovskite with CsPbBr3 quantum dots (QDs). The as-synthesized chiral heterostructure films exhibit obvious circularly polarized luminescence (CPL) properties, even though pure 2D chiral perovskite cannot present photoluminescence. It indicates that the chirality of the excited state of the QDs originates from the 2D chiral perovskite. The circular polarization-resolved transient absorption (TA) spectra further demonstrate that the CPL response of heterostructure films originates from the energy transfer between the chiral perovskite layer and QDs layer and the suppression of spin relaxation, which induces the imbalance of the spin population of excited states in QDs layer. In addition, the photoluminescence (PL), circular dichroism (CD), and CPL spectra of these heterostructure films can be controlled by varying the thickness and component of the chiral perovskite layer, which demonstrates that the anion exchange between chiral perovskite and CsPbBr3 QDs can tune the chemical composition and optoelectronic properties due to the low bonding energy difference between them and decrease the strain within the QDs layer to reduce the radiative recombination lifetime. This work provides guidance for the synthesis of chiral perovskites with a strong CPL response and further provides insight into the origination of CPL.

Constructing Heavy-Atom-Free Photosensitizers for Hypoxic Tumor Phototherapy Based on Donor-Excited Photoinduced Electron-Transfer-Driven Type-I and Type-II Mechanisms.

The spin-orbit charge transfer intersystem crossing (SOCT-ISC) photophysical process has shown great potential for constructing heavy-atom-free photosensitizers (PSs) for photodynamic therapy (PDT) of tumors. However, for almost all such PSs reported to date, the SOCT-ISC is driven by the acceptor-excited photoinduced electron transfer (a-PeT). In this work, for the first time the donor-excited photoinduced electron transfer (d-PeT)-driven SOCT-ISC mechanism is utilized to construct the heavy-atom-free PSs for PDT of tumors by directly installing the electron-deficient N-alkylquinolinium unit (as an electron acceptor) into the meso-position of the near-infrared (NIR) distyryl Bodipy chromophore (as an electron donor). In the less polar environment, the PSs exist as the monomer and promote the production of singlet oxygen (1O2) (Type-II) relying on the d-PeT-driven population of the triplet excited state via SOCT-ISC, whereas in the aqueous environment, they exist as nanoaggregates and induce the generation of superoxides (O2-•) and hydroxyl radicals (HO•) (Type-I) via the d-PeT-driven formation of the delocalized charge-separated state. The PSs could rapidly be internalized into cancer cells and induce the simultaneous production of intracellular 1O2, O2-•, and HO• upon NIR light irradiation, endowing the PSs with superb photocytotoxicity with IC50 values up to submicromolar levels whether under normoxia or under hypoxia. Based on the PSs platform, a tumor-targetable PS is developed, and its abilities in killing cancer cells and in ablating tumors without damage to normal cells/tissues under NIR light irradiation are verified in vitro and in vivo. The study expands the design scope of PSs by introducing the d-PeT conception, thus being highly valuable for achieving novel PSs in the realm of tumor PDT.

Compound-Nucleus and Doorway-State Decays of β-Delayed Neutron Emitters ^{51,52,53}K.

We investigated decays of ^{51,52,53}K at the ISOLDE Decay Station at CERN in order to understand the mechanism of the β-delayed neutron-emission (βn) process. The experiment quantified neutron and γ-ray emission paths for each precursor. We used this information to test the hypothesis, first formulated by Bohr in 1939, that neutrons in the βn process originate from the structureless "compound nucleus." The data are consistent with this postulate for most of the observed decay paths. The agreement, however, is surprising because the compound-nucleus stage should not be achieved in the studied β decay due to insufficient excitation energy and level densities in the neutron emitter. In the ^{53}K βn decay, we found a preferential population of the first excited state in ^{52}Ca that contradicted Bohr's hypothesis. The latter was interpreted as evidence for direct neutron emission sensitive to the structure of the neutron-unbound state. We propose that the observed nonstatistical neutron emission proceeds through the coupling with nearby doorway states that have large neutron-emission probabilities. The appearance of "compound-nucleus" decay is caused by the aggregated small contributions of multiple doorway states at higher excitation energy.

Ultrafast Dynamics of Bloch Surface Wave Polaritons in Large-Area 2D Semiconductor Monolayers at Room Temperature.

The dynamics of strongly coupled polariton systems integrated with 2D transition metal dichalcogenides (TMDs) is key to enabling efficient coherent processes and achieving high-performance TMD-based polaritonic devices, such as ultralow-threshold polariton lasers and ultrafast optical switches. However, there has been a lack of a comprehensive understanding of the excited state dynamics in TMD-based polariton systems. In this work, ultrafast pump-probe optical spectroscopy is used to investigate the room temperature dynamics of the polariton systems consisting of TMD monolayer excitons strongly coupled with Bloch surface waves (BSWs) supported by all-dielectric photonic structures. The transient response is found for both above-exciton energy pumping and polariton-resonant pumping. The excited state population and ultrafast coherent coupling of the exciton reservoir and lower polariton (LP) branch are observed for resonant pumping. Moreover, it is found that the transient response of the LP first decays on a short-time scale of 0.15-0.25ps compared to the calculated intrinsic lifetime of 0.11-0.20ps, and is followed by a longer decay (>100ps) due to the dynamical evolution of the exciton reservoir. The results provide a fundamental understanding of the dynamics of TMD-based polariton systems while showing the potential for achieving efficient coherent optical processes for device applications.

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Optical properties and concentration optimization of Nd: PbF2 crystal for high-energy pulsed laser

Appropriate saturation flux and long fluorescence lifetime are essential requirements for the gain medium in high-energy solid-state laser systems. A novel laser crystal Nd:PbF2 was grown successfully, and the optical performances were evaluated in detail. A theoretically relatively practical method revealing the relationship between the excited state population and doping concentration was developed to guide the optimization of Nd3+ doping concentration. The optical properties of different doping concentrations of Nd:PbF2 single crystals were studied in detail and compared with our theory to demonstrate the accuracy and feasibility of the proposed method. Furthermore, we found that the optimal doping concentration of Nd3+ in the PbF2 crystal was 1 %, with a fluorescence lifetime of 395.3 μs at ∼ 1.06 μm and a saturation flux of 5.8 J/cm2, which is close to the current one is comparable to phosphate glass widely used in nuclear fusion systems, indicating that the 1 % Nd: PbF2 crystal can be used as an excellent gain medium for high-energy lasers.

Symmetry-Breaking Charge Separation Mediated Triplet Population in a Perylenediimide Trimer at the Single-Molecule Level.

Herein, we demonstrate triplet excited-state population in a conformationally rigid perylenediimide trimer (PDI-T) via intramolecular symmetry-breaking charge separation (SB-CS) at the single-molecule level. The single-molecule fluorescence intensity trajectories of PDI-T in nonpolar polystyrene matrix (ε = 2.60) exhibit prolonged fluorescence with infrequent dark states, representing the triplet and/or the charge transfer states. In contrast, in a poly(vinyl alcohol) matrix (ε = 7.80), erratic blinking dynamics resulting in low photon counts were observed, corroborating the feasibility of charge separation in a polar environment. In agreement with the single-molecule measurements, transient absorption spectroscopy of PDI-T reveals ultrafast SB-CS (τCS < 5 ps) in polar tetrahydrofuran (ε = 7.58) and acetone (ε = 20.70), with the population of the triplet excited-state through charge recombination. The current investigation shows the utility of rigid and weakly coupled molecular constructs in controlling triplet generation and SB-CS for potential applications in optoelectronic devices.

Unveiling stellar aurorae: simulating auroral emission lines in hot stars induced by high-energy irradiation

ABSTRACT Auroral emission lines result from the interaction between magnetic field and stellar wind, offering valuable insights into physical properties and processes occurring within magnetospheres of celestial bodies. While extensively studied in planetary and exoplanetary atmospheres, in ultracool dwarfs, and as radio emission from early-type stars, the presence of specific auroral emission lines in hot star spectra remains unexplored. In this study, we utilized tlusty code to simulate the auroral lines, while modelling the effect of the interaction between stellar wind and magnetosphere through X-ray irradiation. Utilizing high-resolution synthetic spectra generated from model atmospheres, we identified potential candidate lines indicative of auroral emission, which were absent in non-irradiated spectra. Emission lines in synthetic spectra were present primarily in the infrared domain. The most prominent line generated by irradiation was He ii 69458 Å, which appeared in all our model atmospheres with effective temperatures ranging from 15 kK to 30 kK. We also calculated the minimum irradiation required to detect emission in this most prominent line. The presence of emission lines was interpreted by considering changes in the population of different excited states of given atoms. Besides the appearance of infrared emission lines, high-energy irradiation causes infrared excess. To complement our simulations, we also searched for auroral lines in Far Ultraviolet Spectroscopic Explorer (FUSE) observations, which are deposited in the Multimission Archive at Space Telescope catalogue. The comparison of observed spectra with synthetic spectra did not identify any possible candidate emission lines in FUSE spectra.

Quantitative analysis of optical emission spectroscopy for plasma process monitoring

In the field of plasma materials processing, various plasma parameters should be evaluated quantitatively and precisely to control the plasma process adequately, particularly with non-invasive methods, one of which is optical emission spectroscopy (OES) measurement. It has sufficient scientific feasibility to derive the electron density N e, electron temperature T e, and the electron energy distribution function (EEDF) even for various processing plasmas in a state of non-equilibrium. In this review, previous studies are reviewed to measure the N e, T e, and EEDF values of argon plasma with low-electron temperature (T e ≃ 1–10 eV) under not only low-pressure conditions but also atmospheric-pressure discharge using the OES measurement. First, to diagnose low-pressure discharge argon plasmas, we explain the basics and applications of the “collisional radiative model”, which models the population kinetics of the excited states in plasma at the elementary process level in non-equilibrium plasma. Methods for analyzing the plasma parameters are shown from the actual measurement results of emission spectra, including machine learning analysis of the excited-state populations. Next, the research results of the method to measure N e, T e, and EEDF are introduced for the measurement of atmospheric-pressure non-equilibrium plasmas using OES measurement of continuum emission, which also includes methods based on machine learning and data-scientific methods for the analysis of the OES data observed as bremsstrahlung of free electrons scattered against neutral molecules.

Protecting the Quantum Coherence of Two Atoms Inside an Optical Cavity by Quantum Feedback Control Combined with Noise-Assisted Preparation

We propose a theoretical scheme to enhance quantum coherence and obtain steady-state coherence by combining quantum feedback control and noise-assisted preparation. We investigate the effects of quantum-jump-based feedback control and noise field on the quantum coherence and excited-state population between two atoms inside an optical cavity where a noise field drives one, and the other is under quantum feedback control. It is found that steady quantum coherence can be achieved by adding an external noise field, and the quantum feedback can prolong the coherence time with partial suppression of the spontaneous emission of atoms. In addition, we study the influence of the joint action of quantum feedback and noise-assisted preparation on quantum coherence and show that the combined action of feedback control and noise-assisted preparation is more effective in enhancing steady coherence. The findings of our research offer some general guidelines for improving the steady-state coherence of coupled qubit systems and have the potential to be applied in the realm of quantum information technology.

Reducing Voltage Losses in Organic Photovoltaics Requires Interfacial Disorder Management

AbstractThanks to the introduction of non‐fullerene acceptors, efficiencies of organic photovoltaics are now approaching 20%. Closing the gap with inorganic photovoltaics requires minimizing voltage losses without penalizing charge extraction, for which microstructure control is crucial. However, the complex interplay between microstructure and charge generation, recombination, and extraction has so far not been unraveled. Here, a systematic study linking device performance to distinct microstructural features via machine learning is presented. Building bi‐layer devices allows to separately study the influence of aggregation and disorder on the energies and lifetimes of bulk and interfacial states. Unambiguous assignments of specific structural motifs to the device photophysics are thus possible. It is found that the control of aggregation‐caused quenching is decisive for the exciton splitting efficiency and thus the carrier generation. Furthermore, the static disorder at the donor–acceptor interface controls the nonradiative recombination by shifting the excited state population from the bulk toward the interface. Finally, the amount of disorder in the bulk is found decisive for charge extraction. The finding that charge generation, recombination, and extraction are controlled by distinct structural features, is the key to optimizing these motifs independently, which will pave the way for organic photovoltaics toward the detailed balance limit.