High-energy States Research Articles

The Interplay of Strongly and Weakly Exchange-Coupled Triplet Pairs in Intramolecular Singlet Fission.

Singlet fission (SF) and triplet-triplet annihilation upconversion (TTA-UC) nominally enable the interconversion of higher-energy singlet states with two lower-energy triplet states and vice versa, with both processes having envisaged application for enhanced solar power devices. The mechanism of SF/TTA-UC involves a complex array of different multiexcitonic triplet-pair states that are coupled by the exchange interaction to varying extents. In this work a family of bounded intramolecular SF materials, based upon the chromophore 1,6-diphenyl-1,3,5-hexatriene, were designed and synthesized. Their SF behavior was characterized using fluorescence lifetime, transient absorption, and magnetic field dependence studies. The capacity for the formation of weakly exchange-coupled triplet pairs, and subsequent spin-evolution, is shown to be strongly dependent upon the combined factors of oligomer size and geometry. By contextualizing these results with the wider SF literature, we present a general schematic model for SF/TTA-UC of greater completeness than portrayed elsewhere.

Energy of functional brain states correlates with cognition in adolescent-onset schizophrenia and healthy persons.

Adolescent-onset schizophrenia (AOS) is rare, under-studied, and associated with more severe cognitive impairments and poorer outcomes than adult-onset schizophrenia. Neuroimaging has shown altered regional activations (first-order effects) and functional connectivity (second-order effects) in AOS compared to controls. The pairwise maximum entropy model (MEM) integrates first- and second-order factors into a single quantity called energy, which is inversely related to probability of occurrence of brain activity patterns. We take a combinatorial approach to study multiple brain-wide MEMs of task-associated components; hundreds of independent MEMs for various sub-systems are fit to 7 Tesla functional MRI scans. Acquisitions were collected from 23 AOS individuals and 53 healthy controls while performing the Penn Conditional Exclusion Test (PCET) for executive function, which is known to be impaired in AOS. Accuracy of PCET performance was significantly reduced among AOS compared to controls. A majority of the models showed significant negative correlation between PCET scores and the total energy attained over the fMRI. Across all instantiations, the AOS group was associated with significantly more frequent occurrence of states of higher energy, assessed with a mixed effects model. An example MEM instance was investigated further using energy landscapes, which visualize high and low energy states on a low-dimensional plane, and trajectory analysis, which quantify the evolution of brain states throughout this landscape. Both supported patient-control differences in the energy profiles. Severity of psychopathology was correlated positively with energy. The MEM integrated representation of energy in task-associated systems can help characterize pathophysiology of AOS, cognitive impairments, and psychopathology.

Observation of reversible conformational interconversion accompanied by 3p internal conversions in Rydberg-excited N,N-dimethylethylamine

Conformational dynamics has been well observed in the 3s Rydberg state of amines, whereas its observation in higher-energy, non-equilibrium 3p Rydberg states is very rare, especially for a reversible conformational transition that could compete with other non-adiabatic transitions. Herein, we report the observation of a reversible conformational interconversion phenomenon in the 3p Rydberg excited-state dynamics of N,N-dimethylethylamine (DMEA). Upon electronic excitation, a forward and backward interconversion between the initially prepared 3p_l and 3p_h conformers accompanied by 3p internal conversions occurs, resulting in a 3p_l/3p_h equilibrium ratio of 61 %/39 % within ∼1.5 ps. The ensuing parallel internal conversions from the 3p_l to 3s_l and 3p_h to 3s_h deposit about 1.80 eV of vibrational energy into the 3s state, enabling a fast conformational interconversion between the 3s_h and 3s_l conformers to proceed within ∼2.0 ps. The final 3s_l/3s_h equilibrium ratio was determined to be 76 %/24 %. This work presents a real-time observation of the entire conformational interconversion process initiating from the higher-energy 3p states and finally reaching an equilibrium on the lower-energy 3s state.

‘Invisible’ Molecular Dynamics Revealed for a Conformationally Chiral π‐Stacked Perylene Bisimide Foldamer

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes ‘invisible’. Here we present an asymmetric perylene bisimide dimer (bis‐PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol–1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re‐fold, the transformation of one stereoisomer into others allowed us to ‘visualize’ the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

'Invisible' Molecular Dynamics Revealed for a Conformationally Chiral π-Stacked Perylene Bisimide Foldamer.

Whilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/vis absorption, fluorescence, and NMR spectroscopy, making such processes 'invisible'. Here we present an asymmetric perylene bisimide dimer (bis-PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥ 116 kJ mol-1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re-fold, the transformation of one stereoisomer into others allowed us to 'visualize' the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleeting metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials.

Transient Leakage Electroluminescence of Quantum-Dot Light-Emitting Diodes.

Parasitic emission or leakage emission caused by electron leakage to a hole transport layer in quantum-dot light-emitting diodes (QLEDs) critically impacts device efficiency and operational stability. The buildup dynamics of such emission channels, however, was insufficiently researched. Herein, we investigate transient electroluminescence dynamics of leakage emission in red/green/blue (R/G/B) QLEDs and reveal notable contrast for R and G. In RQLEDs, leakage emission exhibits delayed turning-on than primary emission, which is attributed to much slower filling up from lower-energy electron states and the initial quenching by nonradiative recombination with trapped holes. For GQLEDs, leakage emission turns on much more concurrently, and emission preferably starts from higher energy states. For R/G QLEDs, under varied offset voltage modulation, the current efficiency of primary emission is invert-correlated to leakage emission, reconfirming leakage emission as a loss indicator.

Investigation of the microstructural characteristics of laser-cladded Ti6Al4V titanium alloy and its corrosion behavior in simulated body fluid

Laser cladding technology has a wide range of potential industrial applications in the surface strengthening, repair and reuse of orthopedic implants. By employing this technique to conduct same-material surface restoration and enhancement on titanium alloys, it demonstrates significant developmental potential. However, the microstructure of laser additively manufactured titanium alloy differs significantly from that of traditional titanium alloys, which affects its corrosion resistance in human body fluids. To compare the corrosion resistance differences between the cladding layer and the substrate, this study investigates the microstructure of multi-pass laser cladding Ti6Al4V (TC4) titanium alloy and analyzes the corrosion morphology and corrosion products of the cladding layer in simulated body fluids (SBF). By comparing the electrochemical corrosion behavior of laser cladding with that of traditionally manufactured TC4, this research reveals the differences in corrosion resistance between the two titanium alloys. The research demonstrates that the microstructure of cladding primarily consists of prior-β grains and continuous grain boundary α phase, along with a complex basketweave structure composed of fine acicular α phase and lamellar α phase. Additionally, due to the complex thermal cycling process, the acicular α' colonies within the prior-β grains. These features enhance the cladding layer’s resistance to plastic deformation and increase microhardness, though with some uneven distribution. Interestingly, the TC4 cladding layer forms a porous passivation layer after corrosion, primarily composed of a TiO2 passivation film and deposits of hydroxyapatite and other phosphates. Due to the lower β-phase content, finer grains with higher energy states, and a greater proportion of high-angle grain boundaries (HAGBs) in the cladding layer, it exhibits higher electrochemical activity. As a result of these microstructural differences, the corrosion resistance of the TC4 cladding layer in SBF is inferior to that of TC4 manufactured using traditional techniques.

Is the Regime Shift in Gulf Stream Warm Core Rings Detected by Satellite Altimetry? An Inter‐Comparison of Eddy Identification and Tracking Products

AbstractDownstream of Cape Hatteras, the vigorously meandering Gulf Stream forms anticyclonic warm core rings (WCRs) that carry warm Gulf Stream and Sargasso Sea waters into the cooler, fresher Slope Sea, and forms cyclonic cold core rings (CCRs) that carry Slope Sea waters into the Sargasso Sea. The Northwest Atlantic shelf and open ocean off the U.S. East Coast have experienced dramatic changes in ocean circulation and water properties in recent years, with significant consequences for marine ecosystems and coastal communities. Some of these changes may be related to a reported regime shift in the number of WCRs formed annually, with a doubling of WCRs shed after 2000. Since the regime shift was detected using a regional eddy‐tracking product, primarily based on sea surface temperatures and relies on analyst skill, we examine three global eddy‐tracking products as an automated and potentially more objective way to detect changes in Gulf Stream rings. Currently, global products rely on altimeter‐measured sea surface height (SSH), with WCRs registering as sea surface highs and CCRs as lows. To identify eddies, these products use either SSH contours or a Lagrangian approach, with particles seeded in satellite‐based surface geostrophic velocity fields. This study confirms the three global products are not well suited for statistical analysis of Gulf Stream rings and suggests that automated WCR identification and tracking comes at the price of accurate identification and tracking. Furthermore, a shift to a higher energy state is detected in the Northwest Atlantic, which coincides with the regime shift in WCRs.

Characterization of Chlorophyll Based Dye-Sensitized Solar Cell using General-Purpose Photovoltaic Device Model

In dye-sensitized solar cells (DSSCs), light is absorbed by the sensitized dye. When light strikes the dye molecule, it absorbs photons and becomes excited to a higher energy state. This excited state allows the dye molecule to inject an electron into the conduction band of the semiconductor, generating an electric current. The selection of dye properties is very significant, as it can help to improve the performance of DSSCs. However, achieving an identical output current-voltage characteristic from the same batch of plants or fruits used as dyes is very difficult. Furthermore, improving the electrical performance, such as short-circuit current density and efficiency, of fabricated dye-sensitized solar cells is critical, as many experimental factors need to be considered. Therefore, to minimize the extra use of material resources due to the risk of unsuccessful fabrications and to obtain better performance ideally, conducting simulation-based studies is important to optimize the performance of DSSCs. The free software General-Purpose Photovoltaic Device Model (GPVDM) is a promising and interesting tool due to its free license and easy accessibility through a graphical interface for simulating optoelectronic devices, including OLEDs, OFETs, and various types of solar cells. This paper considers GPVDM, a 3-D photovoltaic device model, to simulate the proposed structure with different samples of chlorophyll dye for DSSC performance. The paper aims to characterize the high current density-voltage (J-V) of chlorophyll-based DSSCs and identify suitable photovoltaic simulation software for running simulations of chlorophyll-based DSSCs. Finally, the outcomes are compared with experimental data reported in various literature sources. The results show an enhanced short-circuit current density (Jsc) of 0.3556 mA cm-2 for Cordyline fruticose leaves (Chl E), which is the highest among the other dyes tested. The value of simulated short-circuit current density (Jsc) is slightly different from the experimented result Jsc reported in the published paper. In conclusion, GPVDM can be considered suitable for modeling DSSCs.

Atomic-Level Free Energy Landscape Reveals Cooperative Symport Mechanism of Melibiose Transporter.

The Major Facilitator Superfamily (MFS) transporters are an essential class of secondary active transporters involved in various physiological and pathological processes. The melibiose permease (MelB), which catalyzes the stoichiometric symport of the disaccharide melibiose and monovalent cations (e.g., Na+, H+, or Li+), is a key model for understanding the cation-coupled symport mechanisms. Extensive experimental data has established that positive cooperativity between the cargo melibiose and the coupling cation is central to the symport mechanism. However, the structural and energetic origins of this cooperativity remain unclear at the atomistic level for MelB and most other coupled transporters. Here, leveraging recently resolved structures in inward- and outward-facing conformations, we employed the string method and replica-exchange umbrella sampling simulation techniques to comprehensively map the all-atom free energy landscapes of the Na+-coupled melibiose translocation across the MelB in Salmonella enterica serovar Typhimurium (MelBSt), in comparison with the facilitated melibiose transport in a uniporter mutant. The simulation results unravel asymmetrical free energy profiles of melibiose translocation, which is tightly coupled to protein conformational changes in both the N- and C-terminal domains. Notably, the cytoplasmic release of the melibiose induces the simultaneous opening of an inner gate, resulting in a high-energy state of the system. Periplasmic sugar binding and cytoplasmic melibiose released are dynamically coupled with changes in the internal gating elements along the translocation pathway. The outward-facing sugar-bound state is thermodynamically most stable, while the occluded state is a transient state. The binding of Na+ facilitates melibiose translocation by increasing the melibiose-binding affinity and decreasing the overall free energy barrier and change. The cooperative binding of the two substrates results from the allosteric coupling between their binding sites instead of direct electrostatic interaction. These findings add substantial new atomic-level details into how Na+ binding facilitates melibiose translocation and deepen the fundamental understanding of the molecular basis underlying the symport mechanism of cation-coupled transporters.

Signatures of exciton-exciton annihilation in 2DES spectra including up to six-wave mixing processes.

Two-dimensional electronic spectroscopy (2DES) is a powerful spectroscopic tool that allows us to study the dynamics of excited states. Exciton-exciton annihilation is at least a fifth order process, which corresponds to intrachromophoric internal conversion from the double-excited high-energy chromophoric state into the single-excited state of the same chromophore. At high excitation intensities, this effect becomes apparent in standard 2DES and can be inspected via high order nK1⃗-nK2⃗+K3⃗ nonlinear processes. We calculate 2DES based on K1⃗-K2⃗+K3⃗ and 2K1⃗-2K2⃗+K3⃗ wave mixing processes to reveal exciton-exciton annihilation (EEA) induced exciton symmetry breaking, which occurs at high excitation intensities. We present the general theory that captures all these processes for bosonic and paulionic quasiparticles in a unified way and demonstrate that the NEEs can be easily utilized for highly nonlinear two-dimensional spectra calculations by employing phase cycling for separating various phase matching conditions. The approach predicts various excitonic third- to fifth-order features; however, due to high excitation intensities, contributions of different order processes become comparable and overlap, i.e., the signals no longer can be associated with well-defined order-to-the-field contributions. In addition, EEA leads to breaking of the exciton symmetries, thus enabling population of dark excitons. Such effects are due to the local nature of the EEA process.

Tunable Stochastic State Switching in 2D MoS2 Nanomechanical Resonators with Nonlinear Mode Coupling and Internal Resonance.

Coupled nanomechanical resonators have unveiled fascinating physical phenomena, including phonon-cavity coupling, coupled energy decay pathway, avoided crossing, and internal resonance. Despite these discoveries, the mechanisms and control techniques of nonlinear mode coupling phenomena with internal resonances require further exploration. Here, we report on the observation of stochastic switching between the two resonance states with coupled 1:1 internal resonance, for resonant two-dimensional (2D) molybdenum disulfide (MoS2) nanoelectromechanical systems (NEMS), which is directly driven to the critical coupling regime without parametric pumping. We further demonstrate that the probability of state switching is linearly tunable from ∼0% to ∼100% by varying the driving voltage. Furthermore, we gradually increase the white noise amplitude and show that the probability of obtaining the higher-energy state decreases, and the stochastic switching phenomenon eventually disappears. The results provide insights into the dynamics of coupled NEMS resonators and open up new possibilities for sensing and stochastic computing.

A hot-emitter transistor based on stimulated emission of heated carriers

Hot-carrier transistors are a class of devices that leverage the excess kinetic energy of carriers. Unlike regular transistors, which rely on steady-state carrier transport, hot-carrier transistors modulate carriers to high-energy states, resulting in enhanced device speed and functionality. These characteristics are essential for applications that demand rapid switching and high-frequency operations, such as advanced telecommunications and cutting-edge computing technologies1–5. However, the traditional mechanisms of hot-carrier generation are either carrier injection6–11 or acceleration12,13, which limit device performance in terms of power consumption and negative differential resistance14–17. Mixed-dimensional devices, which combine bulk and low-dimensional materials, can offer different mechanisms for hot-carrier generation by leveraging the diverse potential barriers formed by energy-band combinations18–21. Here we report a hot-emitter transistor based on double mixed-dimensional graphene/germanium Schottky junctions that uses stimulated emission of heated carriers to achieve a subthreshold swing lower than 1 millivolt per decade beyond the Boltzmann limit and a negative differential resistance with a peak-to-valley current ratio greater than 100 at room temperature. Multi-valued logic with a high inverter gain and reconfigurable logic states are further demonstrated. This work reports a multifunctional hot-emitter transistor with significant potential for low-power and negative-differential-resistance applications, marking a promising advancement for the post-Moore era.

Simulation of the Pump-Probe Spectra and Excitation Energy Relaxation of the B850 Band of the LH2 Complex in Purple Bacteria.

Ultrafast spectroscopic techniques have been vital in studying excitation energy transfer (EET) in photosynthetic light harvesting complexes. In this paper, we simulate the pump-probe spectra of the B850 band of the light harvesting complex 2 (LH2) of purple bacteria, by using the hierarchical equation of motion method and the optical response function approach. The ground state bleach, stimulated emission, and excited state absorption components of the pump-probe spectra are analyzed in detail. The laser pulse-induced population dynamics are also simulated to help understand the main features of the pump-probe spectra and the EET process. It is shown that the excitation energy relaxation is an ultrafast process with multiple time scales. The first 40 fs of the pump-probe spectra is dominated by the relaxation of the k = ±1 states to both the k = 0 and higher energy states. Dynamics on a longer time scale around 200 fs reflects the relaxation of higher energy states to the k = 0 state.

Polypyrrole incorporated a novel ZnMn2O4 cathode for high-energy quasi-solid state zinc-ion battery

Polypyrrole incorporated a novel ZnMn2O4 cathode for high-energy quasi-solid state zinc-ion battery

Ultrafast Hot Exciton Nonadiabatic Excited-State Dynamics in Green Fluorescent Protein Chromophore Analogue.

The ultrafast high-energy nonadiabatic excited-state dynamics of the benzylidenedimethylimidazolinone chromophore dimer has been investigated using an electronic structure method coupled with on-the-fly quantitative wave function analysis to gain insight into the photophysics of hot excitons in biological systems. The dynamical simulation provides a rationalization of the behavior of the exciton in a dimer after the photoabsorption of light to higher-energy states. The results suggest that hot exciton localization within the manifold of excited states is caused by the hindrance of torsional rotation due to imidazolinone (I) or phenolate (P) bonds i.e., ΦI- or ΦP-dihedral rotation, in the monomeric units of a dimer. This hindrance arises due to weak π-π stacking interaction in the dimer, resulting in an energetically uphill excited-state barrier for ΦI- and ΦP-twisted rotation, impeding the isomerization process in the chromophore. Thus, this study highlights the potential impact of the weak π-π interaction in regulating the photodynamics of the green fluorescent protein chromophore derivatives.

New features in Franck–Hertz experiment with argon: experiment and Monte Carlo simulation

In this work, a homemade apparatus was built to perform the Franck–Hertz experiment with argon. The lowest energy state and the higher energy state of argon can be excited by the Franck–Hertz experiment. The excitation energies of the argon atom are measured by using the setup. The obtained higher excitation energy of argon atoms is 13.73 ± 0.28 eV, for the mixture of higher energy states 3s 23p 53d and 3s 23p 54p. A plate capacitor model was constructed to simulate the inelastic collisions between electrons and argon atoms using the Monte Carlo method. The simulated current curve and electron energy distribution agrees with that of Franck–Hertz experiments, especially the features of higher excited state. The Monte Carlo simulation indicates the deformed electron energy distribution results from the change in excitation proportion of energy levels during the collisions of electrons and argon atoms. Moreover, the new features in Franck–Hertz curve are ascribed to the higher excitation states of argon atoms. The experimental setup has been applied to undergraduate physics experiment teaching in college. Students can perform the Franck–Hertz curve measurement of not only the lowest excited state, but also the higher excited states of argon. In addition, students can do the Monte Carlo simulations for the experimental Franck–Hertz curves and gain a better understanding of electron-argon atom collisions in the experiment. The new designed experiment will make students more familiar with the quantum behavior in atomic physics and quantum mechanics course.

Stepwise Stiffening Chromophore Strategy Realizes a Series of Ultralong Blue Room-Temperature Phosphorescent Materials.

Ultralong room-temperature phosphorescent (URTP) materials have attracted wide attention in anti-counterfeiting, optoelectronic display, and bio-imaging due to their special optical properties. However, room-temperature blue phosphorescent materials are very scarce during applications because of the need to simultaneously populate and stabilize high-energy excited states. In this work, a stepwise stiffening chromophore strategy is proposed to suppress non-radiative jump by continuously reducing the internal spin of the chromophore, and successfully developing a series of blue phosphorescent materials. Phosphorescence lifetimes of more than 3 s are achieved, with the longest lifetime reaching 5.44 s and lasting more than 70 s in the naked eye. As far as is know, this is the best result that has been reported. By adjusting the chromophore conjugation, multicolor phosphorescences from cyan to green have been realized. In addition, these chromophores exhibit the same excellent optical properties in urea and polyvinyl alcohmance (PVA). Finally, these materials are successfully applied to luminescent displays.

Ultrafast generation of hidden phases via energy-tuned electronic photoexcitation in magnetite

Phase transitions occurring in nonequilibrium conditions can evolve through high-energy intermediate states inaccessible via equilibrium adiabatic conditions. Because of the subtle nature of such hidden phases, their direct observation is extremely challenging and requires simultaneous visualization of matter at subpicoseconds and subpicometer scales. Here, we show that a magnetite crystal in the vicinity of its metal-to-insulator transition evolves through different hidden states when controlled via energy-tuned ultrashort laser pulses. By directly monitoring magnetite's crystal structure with ultrafast electron diffraction, we found that upon near-infrared (800 nm) excitation, the trimeron charge/orbital ordering pattern is destroyed in favor of a phase-separated state made of cubic-metallic and monoclinic-insulating regions. On the contrary, visible light (400 nm) activates a photodoping charge transfer process that further promotes the long-range order of the trimerons by stabilizing the charge density wave fluctuations, leading to the reinforcement of the monoclinic insulating phase. Our results demonstrate that magnetite's structure can evolve through completely different metastable hidden phases that can be reached long after the initial excitation has relaxed, breaking ground for a protocol to control emergent properties of matter.

Application of Funnel Metadynamics to the Platelet Integrin αIIbβ3 in Complex with an RGD Peptide.

Integrin αIIbβ3 mediates platelet aggregation by binding the Arginyl-Glycyl-Aspartic acid (RGD) sequence of fibrinogen. RGD binding occurs at a site topographically proximal to the αIIb and β3 subunits, promoting the conformational activation of the receptor from bent to extended states. While several experimental approaches have characterized RGD binding to αIIbβ3 integrin, applying computational methods has been significantly more challenging due to limited sampling and the need for a priori information regarding the interactions between the RGD peptide and integrin. In this study, we employed all-atom simulations using funnel metadynamics (FM) to evaluate the interactions of an RGD peptide with the αIIb and β3 subunits of integrin. FM incorporates an external history-dependent potential on selected degrees of freedom while applying a funnel-shaped restraint potential to limit RGD exploration of the unbound state. Furthermore, it does not require a priori information about the interactions, enhancing the sampling at a low computational cost. Our FM simulations reveal significant molecular changes in the β3 subunit of integrin upon RGD binding and provide a free-energy landscape with a low-energy binding mode surrounded by higher-energy prebinding states. The strong agreement between previous experimental and computational data and our results highlights the reliability of FM as a method for studying dynamic interactions of complex systems such as integrin.