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It is challenging to simulate open quantum systems that are connected to a reservoir through multiple channels. For example, vibrations may induce fluctuations in both energy gaps and electronic couplings, which represent two independent channels of system–bath couplings. Systems of this kind are ubiquitous in the processes of excited state radiationless decay. Combined with density matrix renormalization group (DMRG) and matrix product states (MPS) methods, we develop an interaction-picture chain mapping strategy for vibrational reservoirs to simulate the dynamics of these open systems, resulting in time-dependent spatially local system–bath couplings in the chain-mapped Hamiltonian. This transformation causes the entanglement generated by the system–bath interactions to be restricted within a narrow frequency window of vibrational modes, enabling efficient DMRG/MPS dynamical simulations. We demonstrate the utility of this approach by simulating singlet fission dynamics using a generalized spin-boson Hamiltonian with both diagonal and off-diagonal system–bath couplings. This approach generalizes an earlier interaction-picture chain mapping scheme, allowing for efficient and exact simulation of systems with multi-channel system–bath couplings using matrix product states, which may further our understanding of nonlocal exciton–phonon couplings in exciton transport and the non-Condon effect in energy and electron transfer. [ABSTRACT FROM AUTHOR]

We have synthesized L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots (PQDs) and coupled them with gold nanoparticles (AuNPs). The PQDs and AuNPs, as well as their hybrid nanostructures (HNS), were characterized using UV–visible (UV–vis) and photoluminescence (PL) spectroscopy. The UV–vis spectra show absorption bands of the HNS at 503 and 520 nm, attributed mainly to PQDs and AuNPs, respectively. The PQDs show a strong excitonic PL band peaked at 513 nm from PQDs. The HR-TEM results show the formation of hybrid structures between PQDs and AuNPs, which is also supported by the PL quenching of the PQDs by the coupled AuNPs. Ultrafast dynamics of the exciton and charge carriers in the HNS and pristine PQD were studied using femtosecond transient absorption. Multiexponential fitting of the dynamic data revealed the existence of shallow and deep trap states in pristine PQDs and ultrafast electron transfer from PQDs to AuNPs in the HNS. A kinetic model was proposed to account for the key dynamic processes involved and to extract the time for electron transfer from PQDs to AuNPs in the HNS, found to be ∼2 ps. Dynamic processes in pristine PQDs are largely unchanged by HNS formation with AuNPs. [ABSTRACT FROM AUTHOR]

Strong light–matter coupling within an optical cavity leverages the collective interactions of molecules and confined electromagnetic fields, giving rise to the possibilities of modifying chemical reactivity and molecular properties. While collective optical responses, such as enhanced Rabi splitting, are often observed, the overall effect of the cavity on molecular systems remains ambiguous for a large number of molecules. In this paper, we investigate the non-adiabatic electron transfer process in electron donor–acceptor pairs influenced by collective excitation and local molecular dynamics. Using the timescale difference between reorganization and thermal fluctuations, we derive analytical formulas for the electron transfer rate constant and the polariton relaxation rate. These formulas apply to any number of molecules (N) and account for the collective effect as induced by cavity photon coupling. Our findings reveal a non-monotonic dependence of the rate constant on N, which can be understood by the interplay between electron transfer and polariton relaxation. As a result, the cavity-induced quantum yield increases linearly with N for small N (as predicted by a simple Dicke model) but shows a turnover and suppression for large N. We also interrelate the thermal bath frequency and the number of molecules, suggesting the optimal number for maximizing enhancement. The analysis provides an analytical insight for understanding the collective excitation of light and electron transfer, helping to predict the optimal condition for effective cavity-controlled chemical reactivity. [ABSTRACT FROM AUTHOR]

Owing to their unique optical and electronic properties, vertical van der Waals heterostructures (vdWHs) have attracted considerable attention in optoelectronic applications, such as photodetection, light harvesting, and light-emitting diodes. To fully harness these properties, it is crucial to understand the interfacial charge transfer (CT) and recombination dynamics across vdWHs. However, the effects of interfacial energetics and defect states on interfacial CT and recombination processes in graphene-transition metal dichalcogenide (Gr-TMD) vdWHs remain debated. Here, we investigate the interfacial CT dynamics in Gr-TMD vdWHs with different chemical compositions (W, Mo, S, and Se) and tunable interfacial energetics. We demonstrate, using ultrafast terahertz spectroscopy, that while the photo-induced electron transfer direction is universal with graphene donating electrons to TMDs, its efficiency is chalcogen-dependent: the CT efficiency of S atom-based vdWHs is 3–5 times higher than that of Se-based vdWHs thanks to the lower Schottky barrier present in S-based vdWHs. In contrast, the electron back transfer process from TMD to Gr, which defines the charge separation time, is transition metal-dependent and dominated by the mid-gap defect level of TMDs: W transition metal-based vdWHs possess extremely long charge separation, well beyond 1 ns, which is significantly longer than Mo-based vdWHs with only 10 s of ps charge separation. This difference can be traced to the much deeper mid-gap defect reported in W-based TMDs compared to Mo-based ones, resulting in modified energetics for the back electron transfer from the trapped states to graphene. Our results shed light on the role of interfacial energetics and defects by tailoring chemical compositions of TMDs on the interfacial CT and recombination dynamics in Gr-TMD vdWHs, which is pivotal for optimizing optoelectronic devices, particularly in the field of photodetection. [ABSTRACT FROM AUTHOR]

The chemiresistive effect of an oxide significantly influences its electrical properties, which depend greatly on the interactions between the ambient gas molecules and the solid surface, including the gas adsorption and charge transfer still challenging to be clarified. In this work, we investigate the chemiresistive effect of the p-type delafossite CuScO2 microsheets by comparing their responses to various gaseous alcohols, which increase with an approximately linear relationship with the length of straight carbon chains from methanol to n-hexanol. A new mechanism is proposed to elucidate such a dramatic trend of observed chemiresistive change based on the first-principles calculations and test results. The increasing carbon chain length modulates the adsorption configuration and provides supplementary routes for electron transfer, which is assumed to account for the observed chemiresistive effect. This work may provide a novel perspective for the investigation and development of more advanced functional oxides for electrical applications. [ABSTRACT FROM AUTHOR]

Linker-assisted Ag-TiO2 nanocomposite (NC)-based photocatalysts have been successfully synthesized using thioglycolic acid (TGA) and 3-mercaptopropionic acid (MPA) as bifunctional linker molecules (LMs). The Ag–LMs–TiO2 composites showed greatly improved photocatalytic performance for the degradation of an organic dye mixture under direct sunlight over bare Ag–TiO2 NCs. The efficiencies estimated from the degradation curves for Ag–TiO2, Ag–MPA–TiO2, and Ag–TGA–TiO2 are found to be 82.9%, 90.2%, and 96.1%, respectively. Compared to Ag–MPA–TiO2, Ag–TGA–TiO2 NCs exhibit an enhanced photocatalytic activity, which can be attributed to the TGA molecule's shorter chain length and, hence, faster and more charge transfer, which is duly confirmed by photoluminescence (PL) quenching and TRPL decay curves. Furthermore, higher Stern–Volmer quenching constant values (Ksv) have been obtained for Ag–TGA–TiO2 NCs compared to the bare Ag–TiO2 and Ag–MPA–TiO2 NCs from the PL quenching and estimated Ksv values for Ag–TiO2, Ag–MPA–TiO2, and Ag–TGA–TiO2 are 1400, 1950, and 2560 l−1, respectively. Interestingly, the Ag–TGA–TiO2 recycling analysis confirmed high stability and fast photodegradation up to 40 cycles. From the obtained results, it is concluded that the interfacial electron transfer kinetics in Ag–LM–TiO2 assemblies rely on the length of the alkyl-containing molecular linkers; the shorter the length, the more the charge transfer will be, thereby improving the photocatalytic behavior of the NCs. [ABSTRACT FROM AUTHOR]

Accurate quantum dynamics simulations of nonadiabatic processes are important for studies of electron transfer, energy transfer, and photochemical reactions in complex systems. In this comparative study, we benchmark various approximate nonadiabatic dynamics methods with mapping variables against numerically exact calculations based on the tensor-train (TT) representation of high-dimensional arrays, including TT-KSL for zero-temperature dynamics and TT-thermofield dynamics for finite-temperature dynamics. The approximate nonadiabatic dynamics methods investigated include mixed quantum–classical Ehrenfest mean-field and fewest-switches surface hopping, linearized semiclassical mapping dynamics, symmetrized quasiclassical dynamics, the spin-mapping method, and extended classical mapping models. Different model systems were evaluated, including the spin-boson model for nonadiabatic dynamics in the condensed phase, the linear vibronic coupling model for electronic transition through conical intersections, the photoisomerization model of retinal, and Tully's one-dimensional scattering models. Our calculations show that the optimal choice of approximate dynamical method is system-specific, and the accuracy is sensitively dependent on the zero-point-energy parameter and the initial sampling strategy for the mapping variables. [ABSTRACT FROM AUTHOR]

Electron transfer reactions play an essential role in many chemical and biological processes. Fermi's golden rule (GR), which assumes that the coupling between electronic states is small, has formed the foundation of electron transfer rate theory; however, in short range electron/energy transfer reactions, this coupling can become very large, and, therefore, Fermi's GR fails to make even qualitatively accurate rate predictions. In this paper, I present a simple modified GR theory to describe electron transfer in the Marcus inverted regime at arbitrarily large electronic coupling strengths. This theory is based on an optimal global rotation of the diabatic states, which makes it compatible with existing methods for calculating GR rates that can account for nuclear quantum effects with anharmonic potentials. Furthermore, the optimal GR (OGR) theory can also be combined with analytic theories for non-adiabatic rates, such as Marcus theory and Marcus–Levich–Jortner theory, offering clear physical insights into strong electronic coupling effects in non-adiabatic processes. OGR theory is also tested on a large set of spin-boson models and an anharmonic model against exact quantum dynamics calculations, where it performs well, correctly predicting rate turnover at large coupling strengths. Finally, an example application to a boron-dipyrromethane–anthracene photosensitizer reveals that strong coupling effects inhibit excited state charge recombination in this system, reducing the rate of this process by a factor of 4. Overall, OGR theory offers a new approach to calculating electron transfer rates at strong couplings, offering new physical insights into a range of non-adiabatic processes. [ABSTRACT FROM AUTHOR]

We report the free energy barriers for the elementary reactions in the 2e− and 4e− oxygen reduction reaction (ORR) steps on Au(100) in an alkaline solution. Due to the weak adsorption energy of O2 on Au(100), the barrier for the association channel is very low, and the 2e− pathway is clearly favored, while the barrier for the O–O dissociation channel is significantly higher at 0.5 eV. Above 0.7 V reversible hydrogen electrode (RHE), the association channel becomes thermodynamically unfavorable, which opens up the O–O dissociation channel, leading to the 4e− pathway. The low adsorption energy of oxygenated species on Au is now an advantage, and residue ORR current can be observed up to the 1.0–1.2 V region (RHE). In contrast, the O–O dissociation barrier on Au(111) is significantly higher, at close to 0.9 eV, due to coupling with surface reorganization, which explains the lower ORR activity on Au(111) than that on Au(100). In combination with the previously suggested outer sphere electron transfer to O2 for its initial adsorption, these results provide a consistent explanation for the features in the experimentally measured polarization curve for the alkaline ORR on Au(100) and demonstrate an ORR mechanism distinct from that on Pt(111). It also highlights the importance to consider the spin state of O2 in ORR and to understand the activation barriers, in addition to the adsorption energies, to account for the features observed in electrochemical measurements. [ABSTRACT FROM AUTHOR]

Fullerene–chromophore dyads have attracted a great deal of research interest because these complexes can be potentially designed as nanoscale artificial photosynthetic centers, in which the chromophore and fullerene function as the electron donor and acceptor, respectively. The basic operation of this dyad-type artificial reaction center is photoinduced electron transfer from the donor to the acceptor. The fullerene and chromophore are usually covalently linked so that sufficient electronic coupling between these two moieties can facilitate the electron transfer. However, other deactivation pathways for the chromophore excited state, such as energy transfer to the fullerene, may reduce the quantum yield of the photoinduced electron transfer. Here, a series of C60-perylene dyads is exploited to interrogate the effect of the linkage on deactivation mechanisms of the chromophore excited state. For the C60-perylene dyads with a single or double bond bridge, we find that the decay of the singlet state of the chromophore is dominated by the electron transfer, and the corresponding time constant is determined to be 45 ps. On the other hand, for the dyad with a triple bond bridge, the singlet state of the chromophore is quickly quenched through energy transfer to fullerene, and the time constant is as short as 7.9 ps. Our finding suggests that the bond order of the bridge in the fullerene–chromophore dyads can be utilized to control the deactivation pathways of the excited state. [ABSTRACT FROM AUTHOR]

Uniquely, large-bipolarons' self-trapped holes occupy superoxygens, each comprising four oxygens circumscribed by four coppers in a CuO2 plane, formed as oxygens relax inward and coppers relax outward. Critically, concomitant oxygen-to-copper electron transfer eliminates copper spins. The d-symmetry of superoxygens' ground state molecular orbital tracks the superoxygens' predominant zero-point radial vibrations. These large bipolarons' distinctive charge transport, absorption, magnetism, local atomic vibrations, condensation into a liquid, and subsequent superconductivity are consistent with cuprate superconductors' long-established unusual properties. [ABSTRACT FROM AUTHOR]

We have investigated Interparticle Coulombic Electron Capture (ICEC) using an ab initio approach for two systems, H+ + H2O and H + H2O+. In this work, we have determined the contribution of virtual photon exchange and electron transfer to the total ICEC cross section as a function of the distance between the charged and neutral particles. Furthermore, we have shown that the relative orientation of the electron acceptor and neighbor systems affects the magnitude of the ICEC cross sections by at least two orders at relatively small distances. This geometry dependence, present even for distances as large as 10 a0, is due to the electron transfer contribution. The relative magnitude of each contribution to ICEC seems to depend on the system studied. By replacing the projectile electron with a positron, we have confirmed that electron transfer also takes place in positron collisions and that the charge of the projectile has a noticeable effect on the process, particularly at low scattering energies. [ABSTRACT FROM AUTHOR]

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2 ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100 ps) and electron (∼1 ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures. [ABSTRACT FROM AUTHOR]

Using the density functional theory, we conducted a study on the electrification upon contact between hydrophobic liquid molecules and water molecules, revealing localized characteristics of contact-electrification. These "localized features" refer to the specific microscale characteristics where electron transfer predominantly occurs at the contact regions, influenced by factors such as atomic distances and molecular orientations. Although the electrostatic potential and the highest occupied molecular orbital–lowest unoccupied molecular orbital gap offer substantial predictive insights for electron transfer across polymer interfaces, they fall short in capturing the complexities associated with the interaction between hydrophobic liquids and water molecules. The electronegativity of elements at the interface and the localization of molecular orbitals play a decisive role in electron transfer. Simultaneously, for liquid molecules with irregular structures, there is no correlation between the "contact area" and the amount of electron transfer. The "contact area" refers to the surface region where two different liquid molecules come into close proximity. It is defined by the surface area of atoms with interatomic distances smaller than the van der Waals radius. This study challenges traditional assumptions about contact-electrification, particularly in liquid–liquid interfaces, providing new insights into the localized nature of this phenomenon. [ABSTRACT FROM AUTHOR]

A generalized quantum master equation approach is introduced to describe electron transfer in molecular junctions that spans both the off-resonant (tunneling) and resonant (hopping) transport regimes. The model builds on prior insights from scattering theory but is not limited to a certain parameter range with regard to the strength of the molecule–electrode coupling. The framework is used to study the simplest case of energy and charge transfer between the molecule and the electrodes for a single site noninteracting Anderson model in the limit of symmetric and asymmetric coupling between the molecule and the electrodes. In the limit of elastic transport, the Landauer result is recovered for the current by invoking a single active electron Ansatz and a binary collision approximation for the memory kernel. Inelastic transport is considered by allowing the excitation of electron–hole pairs in the electrodes in tandem with charge transport. In the case of low bias voltages where the Fermi levels of the electrodes remain below the molecular state, it is shown that the current arises from tunneling and the molecule remains neutral. However, once the threshold is reached for aligning the fermi level of one electrode with the molecular orbital, a small amount of charge transfer occurs with a negligible amount of hopping current. While inelasticity in the current has a minimal impact on the shape of the current–voltage curve in the case of symmetric electrode coupling, the results for a slight asymmetry in coupling demonstrate complete charge transfer and a significant drop in current. These results provide encouraging confirmation that the framework can describe charge transport across a wide range of electrode–molecule coupling and provide a unique perspective for developing new master equation treatments for energy and charge transport in molecular junctions. An extension of this work to account for inelastic scattering from electron–vibrational coupling at the molecule is straightforward and will be the subject of subsequent work. [ABSTRACT FROM AUTHOR]

Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties. [ABSTRACT FROM AUTHOR]

We study a moving adsorbate interacting with a metal electrode immersed in a solvent using the time-dependent Newns–Anderson–Schmickler model Hamiltonian. We have adopted a semiclassical trajectory treatment of the adsorbate to discuss the electron and energy transfers that occur between the adsorbate and the electrode. Using Keldysh Green's function scheme, we found a non-adiabatically suppressed electron transfer caused by the motion of the adsorbate and coupling with bath phonons that model the solvent. The energy is thus dissipated into electron–hole pair excitations, which are hindered by interacting with the solvent modes and facilitated by the applied electrode potential. The average energy transfer rate is discussed in terms of the electron friction coefficient and given an analytical expression in the slow-motion limit. [ABSTRACT FROM AUTHOR]

We present cross sections for the formation of positronium chloride (PsCl) in its ground state from the charge exchange between positronium (Ps) and chloride (Cl−) in the range of 10 meV–100 eV Ps energy. We have used theoretical models based on the first Born approximation in its three-body formulation. We simulated the collisions between Ps and Cl− using ab initio binding energies and positronic wave functions at both the mean-field and correlated levels extrapolated to the complete basis set limit. The accuracy of these ab initio data was benchmarked on the PsF system with the existing highly accurate results, including the very recent quantum Monte Carlo results. We have investigated Ps excited states up to n = 4. The results suggest that the channel Ps(n = 2) is of particular interest for the production of PsCl in the ground state and shows that an accurate treatment of correlation effects (i.e., electron–electron and electron–positron correlations) leads to a significant change in the magnitude of the PsCl production cross section with respect to the mean-field level. [ABSTRACT FROM AUTHOR]

We present cross sections for the formation of positronium chloride (PsCl) in its ground state from the charge exchange between positronium (Ps) and chloride (Cl−) in the range of 10 meV–100 eV Ps energy. We have used theoretical models based on the first Born approximation in its three-body formulation. We simulated the collisions between Ps and Cl− using ab initio binding energies and positronic wave functions at both the mean-field and correlated levels extrapolated to the complete basis set limit. The accuracy of these ab initio data was benchmarked on the PsF system with the existing highly accurate results, including the very recent quantum Monte Carlo results. We have investigated Ps excited states up to n = 4. The results suggest that the channel Ps(n = 2) is of particular interest for the production of PsCl in the ground state and shows that an accurate treatment of correlation effects (i.e., electron–electron and electron–positron correlations) leads to a significant change in the magnitude of the PsCl production cross section with respect to the mean-field level. [ABSTRACT FROM AUTHOR]

In view of the inherent pseudocapacitance, rich redox pairs (Nb5+/Nb4+ and Nb4+/Nb3+), and high lithiation potential (1.0–3.0 V vs Li/Li+), Nb2O5 is considered a promising anode material. However, the inherent low electronic conductivity of Nb2O5 limits its lithium storage performance, and the rate performance after carbon modification is still unsatisfactory because the intrinsic conductivity of Nb2O5 has not been substantially improved. In this experiment, taking the improvement of the intrinsic electrical conductivity of Nb2O5 as the guiding ideology, we prepared F-doped Nb2O5@fluorocarbon composites (F–Nb2O5@FC) with a large number of oxygen vacancies by one-step annealing. As the anode electrode of lithium-ion batteries, the reversible specific capacity of F–Nb2O5@FC reaches 150 mA g−1 at 5 A g−1 after 1100 cycles, and the rate performance is particularly outstanding, with a capacity up to 130 mA g−1 at 16 A g−1, which is far superior to other Nb2O5@carbon-based anode electrodes. Compared with other single conductivity sources of Nb2O5@carbon-based composites, the electrical conductivity of F–Nb2O5@FC composites is greatly improved in many aspects, including the introduction of free electrons by F− doping, the generation of oxygen vacancies, and the provision of a three-dimensional conductive network by FC. Through analytical chemistry (work function, UV–Vis diffuse reflectance spectroscopy, and EIS) and theoretical calculations, it is proved that F–Nb2O5@FC has high electrical conductivity and realizes rapid electron transfer. [ABSTRACT FROM AUTHOR]

The entanglement between system and bath often plays a pivotal role in complex systems spanning multiple orders of magnitude. A system–bath entanglement theorem was previously established for Gaussian environments in J. Chem. Phys. 152, 034102 (2020) regarding linear response functions. This theorem connects the entangled responses to the local system and bare bath properties. In this work, we generalize it to correlation functions. Key steps in derivations involve using the generalized Langevin dynamics for hybridizing bath modes and the Bogoliubov transformation that maps the original finite-temperature reservoir to an effective zero-temperature vacuum by employing an auxiliary bath. The generalized theorem allows us to evaluate the system–bath entangled correlations and the bath mode correlations in the total composite space, as long as we know the bare-bath statistical properties and obtain the reduced system correlations. To demonstrate the cross-scale entanglements, we utilize the generalized theorem to calculate the solvation free energy of an electron transfer system with intramolecular vibrational modes. [ABSTRACT FROM AUTHOR]

It is a novel-effective process for realizing high-efficiency sensing and continuous gas monitoring by introducing precious metals into metal–oxide–semiconductors (MOSs). In this study, Ag is exploited to prepare surface functionalized SnO2 nanoparticles (NPs) and innovative xAg@SnO2/CsPbBr3, activating and catalyzing the gas sensing reactions on semiconductors. The results show that the precious metal Ag NPs promote the directional transport of carriers, thus improving the gas sensing performances. In addition, innovative xAg@SnO2/CsPbBr3 composites originated from Ag@SnO2 NPs and 3-mercaptopropionic acid treated all-inorganic perovskite CsPbBr3 are constructed to further accelerate electron transfer on heterointerfaces, enabling continuous and efficient monitoring of ethanolamine (EA) at room temperature. The sensing properties of Ag@SnO2/CsPbBr3 on various volatile organic compounds are investigated. Compared with pure CsPbBr3, the EA response of as-prepared 2Ag@SnO2/CsPbBr3 is obviously improved by about sevenfold. The response/recovery time is greatly shortened, besides the good stability. Another interesting result for xAg@SnO2/CsPbBr3 is the lower limit of detection of 44.43 ppb. The work demonstrates that Ag modification facilitates the adsorption/desorption rate and the response. Furthermore, the catalytic activation of noble metal Ag NPs and the synergistic interaction of SnO2/CsPbBr3 nano-heterojunctions promote EA sensing performances at room temperature. [ABSTRACT FROM AUTHOR]

Diffusion of electrons over distances on the order of 100 μm has been observed in crystals of a small tetraheme cytochrome (STC) from Shewanella oneidensis [J. Huang et al. J. Am. Chem. Soc. 142, 10459–10467 (2020)]. Electron transfer between hemes in adjacent subunits of the crystal is slower and more strongly dependent on temperature than had been expected based on semiclassical electron-transfer theory. We here explore explanations for these findings by molecular-dynamics simulations of crystalline and monomeric STC. New procedures are developed for including time-dependent quantum mechanical energy differences in the gap between the energies of the reactant and product states and for evaluating fluctuations of the electronic-interaction matrix element that couples the two hemes. Rate constants for electron transfer are calculated from the time- and temperature-dependent energy gaps, coupling factors, and Franck–Condon-weighted densities of states using an expression with no freely adjustable parameters. Back reactions are considered, as are the effects of various protonation states of the carboxyl groups on the heme side chains. Interactions with water are found to dominate the fluctuations of the energy gap between the reactant and product states. The calculated rate constant for electron transfer from heme IV to heme Ib in a neighboring subunit at 300 K agrees well with the measured value. However, the calculated activation energy of the reaction in the crystal is considerably smaller than observed. We suggest two possible explanations for this discrepancy. The calculated rate constant for transfer from heme I to II within the same subunit of the crystal is about one-third that for monomeric STC in solution. [ABSTRACT FROM AUTHOR]

Experimental findings by others suggest that OH radicals are formed in unexpected abundance on or near surfaces of 1–50 µm microdroplets comprised of pure water, but the mechanism by which these radicals are generated is not yet fully resolved. In this work, we examine two possibilities using ab initio electronic structure methods: (1) electron transfer (ET) from a microdroplet surface-bound OH− anion to a nearby H3O+ cation and (2) proton transfer (PT) from such a H3O+ cation to a nearby OH− anion. Our findings suggest that both processes are possible but only if the droplet's underlying water molecules comprising the microdroplet provide little screening of the Coulomb interaction between the anion and cation once they reach ∼10 Å of one another. In the ET event, an OH radical is formed directly; for PT, the OH formation occurs because the new O–H bond formed by the transferred proton is created at a bond length sufficiently elongated to permit homolytic cleavage. Both the ET and PT pathways predict that H atoms will also be formed. Finally, we discuss the roles played by strong local electric fields in mechanisms that have previously been proposed and that occur in our two mechanisms. [ABSTRACT FROM AUTHOR]

Interfacial electron transfer (IET) through saturated single-linker and dual-linker groups from a perylene chromophore into nanostructured TiO2 films was studied by ultrafast spectroscopy. Perylene chromophores with one and two propanoic acid linker groups in the peri and ortho positions were investigated. In comparison to previously studied perylenes bound via unsaturated acrylic acid linkers, the chromophores with saturated linkers showed bi-exponential IET dynamics. Two distinct transfer times were observed that indicate the presence of two concurrent binding modes. A comparison between ortho- and peri-substituted sensitizers resulted in slower IET dynamics and weaker electronic coupling for ortho substitution. Finally, IET from sensitizers with saturated linker groups is neither promoted nor hindered by a second linker group. This indicates that only one of the two linkers binds covalently to the surface. This study reveals the importance of the anchor-binding mode and design considerations of the linker for regulating IET. [ABSTRACT FROM AUTHOR]

The activation volume, which quantifies the response of the chemical reactions to the applied stress, plays a central role in controlling the mechanochemical reactions for applications including lubricity, wear, and the topographic fabrication of the surfaces under stress. However, the physical interpretations of the activation volume remain scientifically intriguing and largely unexplored. Here, density functional theory calculations are used to investigate the general rules of charge transfer underlying activation volume in controlling the typically mechanochemical reaction process. It is found that the activation volume could be decoupled into the electronic contributions from interface chemistry and bulk physical deformation, which are commonly linear dependent on the contact pressure. Therefore, the activation volume may, indeed, be derived from the stress-driven charge transfer underlying cooperative competition between interfacial chemistry and the bulk region. This competition is related to the stiffness change from the bulk to slab. The magnitude of the stiffness change represents the degree to which the interface atoms modify the bulk properties, which is directly related to the contribution of different regions to the activation volume. This work may open up the understanding of the activation volume from dynamic electron transfer to engineer mechanochemical reactions, different from the existing insights into the geometric dimensionality of the contact configuration. [ABSTRACT FROM AUTHOR]

In recent years, organic–inorganic hybrid perovskite (PVK) devices have attracted widespread attention with their high absorption coefficient and low-cost fabrication process. Formamidinium lead iodide (FAPbI3) perovskite solar cells (PSCs) have been reported to obtain high power conversion efficiencies (PCEs) due to the narrow bandgap. Zinc oxide (ZnO) has better electrical conductivity and high transmittance than tin (IV) dioxide (SnO2). However, the deprotonation behavior of ZnO limits its use in formamidinium (FA) or methylammonium (MA) devices, so it is mostly used in all-inorganic PSCs. In this work, to avoid the deprotonation behavior of ZnO, we prepared FAPbI3 PSCs using ZnO/SnO2 as bilayer electron transporting layers (ETLs), which improved the conductivity of the ETLs and promoted electron extraction and transfer. In addition, the decrease in the oxygen vacancy (Ov) on the bilayer ETLs contributed to the suppression of the non-radiative recombination of the device, thus enabling the achievement of a higher fill factor. As a result, the modified ETLs increased the PCE of FAPbI3 PSCs from 20.24% to 21.42% and improved the stability of the devices. The PCE of unpackaged devices increased steadily to 21.91% when stored in an N2 atmosphere for 183 days. [ABSTRACT FROM AUTHOR]

The ultrafast photoinduced electron or exciton transfer was investigated theoretically. The charge separation on the ultrafast time scale results in the unrelaxed vibrational modes that appear in the initial terms of the generalized master equations. Here, the impact of these initial terms on the electron transfer directionality in the open system was evaluated. Moreover, the role of unrelaxed vibrational modes in electron–hole separation was also examined. It was shown that the unrelaxed vibrational modes significantly increase the efficiency of electron–hole separation. This could play a crucial role in the remarkable efficiency of charge separation in biological systems. [ABSTRACT FROM AUTHOR]

The physical regions (domains or basins) within the molecular structure are open systems that exchange charge between them and, consequently, house a fractional number of electrons (net charge). The natural framework describing the quantum states for these domains is the density matrix (DM) in its grand-canonical version, which corresponds to a convex expansion into a set of basis states of an integer number of electrons. In this report, it is shown that the solution for these quantities is supported by the DM expansion into three states of different numbers of particles: the neutral and two (edge) ionic states. The states and the average number of particles in the domains (fractional occupation population) are determined by the coefficients of the expansion in terms of the fundamental transference magnitudes, revealing the donor/acceptor character of the domains by which the quantum accessible states are discussed. [ABSTRACT FROM AUTHOR]

Intramolecular electron transfer between two biphenyl groups linked by an androstane spacer and excitation of the pyridinium-N-phenolate betaine dye B30 to the first excited singlet state are studied by quantum/classical molecular-dynamics simulations at temperatures between 150 and 300 K in solvents with a range of polarities. Temperature dependences of the solvent reorganization energies, free energies, entropies, and the inhomogeneous broadening of B30's absorption band are examined. The variances of fluctuations of the energy gap between the reactant and product states do not have the direct proportionality to temperature that often is assumed to hold. An explanation for the observations is suggested. [ABSTRACT FROM AUTHOR]

Metal-reducing bacteria have adapted the ability to respire extracellular solid surfaces instead of soluble oxidants. This process requires an electron transport pathway that spans from the inner membrane, across the periplasm, through the outer membrane, and to an external surface. Multiheme cytochromes are the primary machinery for moving electrons through this pathway. Recent studies show that the chiral-induced spin selectivity (CISS) effect is observable in some of these proteins extracted from the model metal-reducing bacteria, Shewanella oneidensis MR-1. It was hypothesized that the CISS effect facilitates efficient electron transport in these proteins by coupling electron velocity to spin, thus reducing the probability of backscattering. However, these studies focused exclusively on the cell surface electron conduits, and thus, CISS has not been investigated in upstream electron transfer components such as the membrane-associated MtrA, or periplasmic proteins such as small tetraheme cytochrome (STC). By using conductive probe atomic force microscopy measurements of protein monolayers adsorbed onto ferromagnetic substrates, we show that electron transport is spin selective in both MtrA and STC. Moreover, we have determined the spin polarization of MtrA to be ∼77% and STC to be ∼35%. This disparity in spin polarizations could indicate that spin selectivity is length dependent in heme proteins, given that MtrA is approximately two times longer than STC. Most significantly, our study indicates that spin-dependent interactions affect the entire extracellular electron transport pathway. [ABSTRACT FROM AUTHOR]

Designing organic semiconductors for practical applications in organic solar cells, organic field-effect transistors, and organic light-emitting diodes requires understanding charge transfer mechanisms across different length and time scales. The underlying electron transfer mechanisms can be efficiently explored using semiempirical quantum mechanical (SQM) methods. The dimer projection (DIPRO) method combined with the recently introduced non-self-consistent density matrix tight-binding potential (PTB) [Grimme et al., J. Chem. Phys. 158, 124111 (2023)] is used in this study to evaluate charge transfer integrals important for understanding charge transport mechanisms. PTB, parameterized for the entire Periodic Table up to Z = 86, incorporates approximate non-local exchange, allowing for efficient and accurate calculations for large hetero-organic compounds. Benchmarking against established databases, such as Blumberger's HAB sets, or our newly introduced JAB69 set and comparing with high-level reference data from ωB97X-D4 calculations confirm that DIPRO@PTB consistently performs well among the tested SQM approaches for calculating coupling integrals. DIPRO@PTB yields reasonably accurate results at low computational cost, making it suitable for screening purposes and applications to large systems, such as metal-organic frameworks and cyanine-based molecular aggregates further discussed in this work. [ABSTRACT FROM AUTHOR]

The nitrogen-vacancy (NV) centers (NCVSi)− in 4H silicon carbide (SiC) constitute an ensemble of spin S = 1 solid state qubits interacting with the surrounding 14N and 29Si nuclei. As quantum applications based on a polarization transfer from the electron spin to the nuclei require the knowledge of the electron–nuclear interaction parameters, we have used high-frequency (94 GHz) electron–nuclear double resonance spectroscopy combined with first-principles density functional theory to investigate the hyperfine and nuclear quadrupole interactions of the basal and axial NV centers. We observed that the four inequivalent NV configurations (hk, kh, hh, and kk) exhibit different electron–nuclear interaction parameters, suggesting that each NV center may act as a separate optically addressable qubit. Finally, we rationalized the observed differences in terms of distinctions in the local atomic structures of the NV configurations. Thus, our results provide the basic knowledge for an extension of quantum protocols involving the 14N nuclear spin. [ABSTRACT FROM AUTHOR]

In this computational study, we describe a self-consistent trajectory simulation approach to capture the effect of neutral gas pressure on ion–ion mutual neutralization (MN) reactions. The electron transfer probability estimated using Landau–Zener (LZ) transition state theory is incorporated into classical trajectory simulations to elicit predictions of MN cross sections in vacuum and rate constants at finite neutral gas pressures. Electronic structure calculations with multireference configuration interaction and large correlation consistent basis sets are used to derive inputs to the LZ theory. The key advance of our trajectory simulation approach is the inclusion of the effect of ion-neutral interactions on MN using a Langevin representation of the effect of background gas on ion transport. For H+ − H− and Li+ − H(D)−, our approach quantitatively agrees with measured speed-dependent cross sections for up to ∼105 m/s. For the ion pair Ne+ − Cl−, our predictions of the MN rate constant at ∼1 Torr are a factor of ∼2 to 3 higher than the experimentally measured value. Similarly, for Xe+ − F− in the pressure range of ∼20 000–80 000 Pa, our predictions of the MN rate constant are ∼20% lower but are in excellent qualitative agreement with experimental data. The paradigm of using trajectory simulations to self-consistently capture the effect of gas pressure on MN reactions advanced here provides avenues for the inclusion of additional nonclassical effects in future work. [ABSTRACT FROM AUTHOR]

For a detailed understanding of many processes in nature involving, for example, energy or electron transfer, the theory of open quantum systems is of key importance. For larger systems, an accurate description of the underlying quantum dynamics is still a formidable task, and, hence, approaches employing machine learning techniques have been developed to reduce the computational effort of accurate dissipative quantum dynamics. A downside of many previous machine learning methods is that they require expensive numerical training datasets for systems of the same size as the ones they will be employed on, making them unfeasible to use for larger systems where those calculations are still too expensive. In this work, we will introduce a new method that is implemented as a machine-learned correction term to the so-called Numerical Integration of Schrödinger Equation (NISE) approach. It is shown that this term can be trained on data from small systems where accurate quantum methods are still numerically feasible. Subsequently, the NISE scheme, together with the new machine-learned correction, can be used to determine the dissipative quantum dynamics for larger systems. Furthermore, we show that the newly proposed machine-learned correction outperforms a previously handcrafted one, which, however, improves the results already considerably. [ABSTRACT FROM AUTHOR]

In this study, the electronic engineering of a high-valent active site for enhanced oxygen evolution reaction (OER) was achieved through the electrochemical pre-cathodic treatment method (EPCTM). This method involves applying a cathodic potential to the drop-cast working electrode of Mn-substituted nickel ferrite (Ni1−xMnxFe2O4; where x = 0.0, 0.2, and 0.4) electrocatalysts. X-ray photoelectron spectroscopy analysis revealed an increase in the ratios of Ni3+/Ni2+ and Mn3+/Mn2+ in Ni1−xMnxFe2O4 after EPCTM followed by OER, leading to an enhancement in electrochemical OER current density at 600 mV overpotential by 3.65 times for x = 0.0, 5.56 times for x = 0.20, and 4.72 times for x = 0.40. This enhancement was further supported by a decrease in the slope of the anodic Tafel equation after EPCTM, indicating improved efficiency of the interaction between the working electrode and electrolyte, as a lower Tafel slope suggests better charge exchange at the electrode–electrolyte interface. The positive slope in the Mott–Schottky (MS) plot for all Ni1−xMnxFe2O4 samples confirmed the p-type nature of the electrocatalysts. Additionally, the significant decrease in the slope of the linear portion of the MS plot indicated an increase in carrier concentration after electrochemical pre-cathodic treatment in all Ni1−xMnxFe2O4 samples. This increase in p-type carrier concentration supports the observed increase in the Ni3+/Ni2+ ratio for OER after EPCTM. [ABSTRACT FROM AUTHOR]

The use of the organic semiconductor copper hexadecafluorophthalocyanine (F16CuPc) in WSe2 based heterostructure field-effect transistors (FETs) is shown to result in a large reduction in electron current while not significantly impacting the hole current. This approach is promising for use in p-channel FETs in which electron transport is undesirable and increases leakage currents and power dissipation in the off-state. The reduction in on-state electron currents, by up to three orders of magnitude, is due to the transfer of electrons to the low-mobility states in F16CuPc due to the greater electron affinity of the organic semiconductor compared to WSe2. The off-state currents under a drain bias are reduced by more than four orders of magnitude due to the effective suppression of electron currents. This is a result of the formation of type II heterostructure between F16CuPc and WSe2. Electrons in this heterostructure FET will preferentially transfer to F16CuPc, while holes will tend to remain in the high mobility WSe2 layer. This effect is more marked in monolayer WSe2 based FETs compared to multilayer WSe2 FETs due to a larger difference in electron affinities with respect to F16CuPc. Also, the magnitude of electron current suppression was further enhanced when F16CuPc is deposited only on a part of the channel near the source of WSe2 +F16CuPc FETs. [ABSTRACT FROM AUTHOR]

We report an experimental investigation on the effect of ground-state charge transfer and its induced electric field on photoexcited charge transfer in van der Waals heterostructures. Two heterostructure samples were fabricated by stacking an undoped WSe2 monolayer with either a Nb-doped or undoped MoSe2 monolayer. While no ground-state charge transfer is expected in the MoSe2/WSe2 heterostructure, the doped holes in the MoSe2:Nb/WSe2 heterostructure can transfer to WSe2, creating a space-charge electric field. By comparing the photoluminescence and time-resolved differential reflectance of the two heterostructures, we find that photoexcited hole transfer from MoSe2 to WSe2 is largely blocked by this field, whereas photoexcited electron transfer from WSe2 to MoSe2 is less affected. These results provide insight into the impact of doping on the charge-transfer performance of van der Waals heterostructures. [ABSTRACT FROM AUTHOR]

Sodium-ion batteries (SIBs) have been widely researched due to their abundant resource and inherent safety. However, the major challenge for further commercialization of SIBs is the absence of low-priced anode electrodes with high reversible capacity and durability. Herein, a hierarchical heterogeneous structure of FeS2/SnS2@C nanocubes with rich two-dimensional mosaic-like heterointerface and N/S co-doped carbon wrapping is constructed and synthesized, to achieve ultrahigh reversible capacity and long cycling stability as anode of SIBs. Combining x-ray photoelectron spectroscopy, ion diffusion kinetic analysis, and in situ x-ray diffraction, the exquisite hierarchical heterogeneous structure of FeS2/SnS2@C could promote charge/electrons transfer and accelerate ion diffusion kinetics. As expected, the FeS2/SnS2@C anode shows superior reversible capacity (867.5 mA h g−1 at 0.1 A g−1), good rate performance (718.9 mA h g−1 at 5.0 A g−1), and long cycle stability (738.0 mA h g−1 after 1200 cycles at 5.0 A g−1) with Na metal as counter electrode. This work proves that the effectiveness of heterojunction interfaces for promoting Na+ diffusion is highlighted by such capabilities. [ABSTRACT FROM AUTHOR]

Here, we present a novel spectroscopy approach to investigate impurity transport by analyzing line-radiation following high-n Rydberg transitions. While high-n Rydberg states of impurity ions are unlikely to be populated via impact excitation, they can be accessed by charge exchange (CX) reactions along the neutral beams in high-temperature plasmas. Hence, localized radiation of highly ionized impurities, free of passive contributions, can be observed at multiple wavelengths in the visible range. For the analysis and modeling of the observed Rydberg transitions, a technique for calculating effective emission coefficients is presented that can well reproduce the energy dependence seen in datasets available on the OPEN-ADAS database. By using the rate coefficients and comparing modeling results with the new high-n Rydberg CX measurements, impurity transport coefficients are determined with well-documented 2σ confidence intervals for the first time. This demonstrates that high-n Rydberg spectroscopy provides important constraints on the determination of impurity transport coefficients. By additionally considering Bolometer measurements, which provide constraints on the overall impurity emissivity and, therefore, impurity densities, error bars can be reduced even further. [ABSTRACT FROM AUTHOR]

A set of two newly designed, single-channel Czerny–Turner spectrometers has been deployed at the DIII-D tokamak for measurements of the motional Stark effect (MSE) split beam emission and the C6+ (CVI) carbon charge exchange recombination (CER) emission at high spectral (δλ = 0.13 nm) and temporal (1–5 kHz) resolution. High throughput optics (f/# = 2.8) allow for good signal-to-noise at high time resolution using fast EMCCD detectors. The MSE emission allows for spectral fitting of the magnitude and direction of the local B-field, while the carbon emission yields local ion temperature and toroidal rotation information. To reduce so-called Doppler broadening of the MSE emission, a new channel-specific variable lens-masking approach has been developed. Experimental data collected from the 2023 DIII-D experimental campaign demonstrate the signal quality and instrument fidelity for both diagnostic measurements. Moreover, initial CER data analysis shows a clear evolution of the toroidal rotation during edge localized modes. Initial progress on the advanced MSE model, including a new validated ray-trace model of the DIII-D collection optics, is shown via sensitivity analysis. [ABSTRACT FROM AUTHOR]

A 16 channel spectroscopy system has been installed on DIII-D to provide information about the energy distribution of the atomic neutrals using the Doppler shift and broadening of passive Balmer-α emission. The lines of sight are dominantly in the toroidal direction, with tangencies near the lowest point on closed magnetic flux surfaces moving from the lower divertor upward into the confined plasma. This allows the system to provide details of the neutrals as they undergo various atomic physics processes while traveling upward from the lower divertor. The spectrally resolved measurements provide several advantages that complement typical optical filter based measurements of hydrogenic spectral lines. These include more direct measurements of the neutrals that fuel deeper in the plasma and capturing neutral velocity distribution information via the Doppler broadened and shifted line. In addition, the spectral separation of higher energy "thermal" neutrals and bright cold emission from the scrape-off layer allows for a more straightforward calculation of the underlying neutral densities based on the emission because of the dependence of the thermal emission on confined plasma properties that are approximately flux functions and well measured. [ABSTRACT FROM AUTHOR]

While the electron transport barrier remains in its final form before an edge-localized mode crash, edge turbulence manifests as fluctuations in electron temperature. Because edge turbulence is closely related to the evolution and collapse of pedestal, the microscopic spatial structure and dynamics of electron temperature fluctuations during the electron temperature pedestal evolution phase are studied using broadband electron cyclotron emission measurements. The cross phase between the electron temperature and potential fluctuations is evaluated using a velocimetry technique to identify the nature of turbulence. A comprehensive comparison of the properties of various instabilities confirms that the micro-tearing mode is a leading candidate associated with the electron temperature pedestal evolution and collapse. The quadratic transfer function reveals that the energy within the pedestal is nonlinearly transferred to the interior of the electron temperature pedestal before the pedestal collapse, resulting in radial change in the mode structure and dynamics. [ABSTRACT FROM AUTHOR]

Investigating the role of chiral-induced spin selectivity in the generation of spin correlated radical pairs in a photoexcited donor–chiral bridge–acceptor system is fundamental to exploit it in quantum technologies. This requires a minimal master equation description of both charge separation and recombination through a chiral bridge. To achieve this without adding complexity and entering in the microscopic origin of the phenomenon, we investigate the implications of spin-polarizing reaction operators to the master equation. The explicit inclusion of coherent evolution yields non-trivial behaviors in the charge and spin dynamics of the system. Finally, we apply this master equation to a setup comprising a molecular qubit attached to the donor–bridge–acceptor molecule, enabling qubit initialization, control, and read-out. Promising results are found by simulating this sequence of operations assuming realistic parameters and achievable experimental conditions. [ABSTRACT FROM AUTHOR]

Exciplexes are excited-state complexes formed as a result of partial charge transfer from the donor to the acceptor species when one moiety of the donor–acceptor pair is electronically excited. The arene–amine exciplex formed between oligo-(p-phenylene) (OPP) and triethylamine (TEA) is of interest in the catalytic photoreduction of CO2 because it can compete with complete electron transfer to the OPP catalyst. Therefore, formation of the exciplex can hinder the generation of a radical anion OPP·− necessary for subsequent CO2 reduction. We report an implementation of a workflow automating quantum-chemistry calculations that generate and characterize an ensemble of structures to represent this exciplex state. We use FireWorks, Pymatgen, and Custodian Python packages for high-throughput ensemble generation. The workflow includes time-dependent density functional theory optimization, verification of excited-state minima, and exciplex characterization with natural transition orbitals, exciton analysis, excited-state Mulliken charges, and energy decomposition analysis. Fluorescence spectra computed for these ensembles using Boltzmann-weighted contributions of each structure agree better with experiment than our previous calculations based on a single representative exciplex structure [Kron et al., J. Phys. Chem. A 126, 2319–2329 (2022)]. The ensemble description of the exciplex state also reproduces an experimentally observed red shift of the emission spectrum of [OPP-4–TEA]* relative to [OPP-3–TEA]*. The workflow developed here streamlines otherwise labor-intensive calculations that would require significant user involvement and intervention. [ABSTRACT FROM AUTHOR]

In this research, we explore sequence-dependent chiral-induced spin selectivity (CISS) in double-stranded (ds)-DNA using time-correlated single-photon counting and electrochemical impedance spectroscopy supplemented by tight-binding calculations of the phenomenon for the first time. The average lifetime of the photo-excited electrons in a Quantum Dot-DNA system is influenced by the CISS effect generated by the DNA molecule, and the difference in average time decay of electrons was found to be 345 ps for opposite polarity ("UP" and "DOWN") of spins due to the CISS effect. Moreover, the yield of spin-polarized electrons due to the CISS effect was reduced by more than 35% from perfect DNA to DNA with point mutations. Remarkably, by employing a tight binding method combined with Green's function formalism for transport, simulations of the process support the observed experimental trends. Our results provide a basic understanding of the sequence-specific spin-dependent electron transfer through ds-DNA. These results would help to build spin-based next-generation DNA sensors. [ABSTRACT FROM AUTHOR]

Controlling matter at the level of electrons using ultrafast laser sources represents an important challenge for science and technology. Recently, we introduced a general laser control scheme (the Stark control of electrons at interfaces or SCELI) based on the Stark effect that uses the subcycle structure of light to manipulate electron dynamics at semiconductor interfaces [A. Garzón-Ramírez and I. Franco, Phys. Rev. B 98, 121305 (2018)]. Here, we demonstrate that SCELI is also of general applicability in molecule–semiconductor interfaces. We do so by following the quantum dynamics induced by non-resonant few-cycle laser pulses of intermediate intensity (non-perturbative but non-ionizing) across model molecule–semiconductor interfaces of varying level alignments. We show that SCELI induces interfacial charge transfer regardless of the energy level alignment of the interface and even in situations where charge exchange is forbidden via resonant photoexcitation. We further show that the SCELI rate of charge transfer is faster than those offered by resonant photoexcitation routes as it is controlled by the subcycle structure of light. The results underscore the general applicability of SCELI to manipulate electron dynamics at interfaces on ultrafast timescales. [ABSTRACT FROM AUTHOR]

Electron transfer (ET) is a fundamental process in chemistry and biochemistry, and electronic coupling is an important determinant of the rate of ET. However, the electronic coupling is sensitive to many nuclear degrees of freedom, particularly those involved in intermolecular movements, making its characterization challenging. As a result, dynamic disorder in electron transfer coupling has rarely been investigated, hindering our understanding of charge transport dynamics in complex chemical and biological systems. In this work, we employed molecular dynamic simulations and machine-learning models to study dynamic disorder in the coupling of hole transfer between neighboring ethylene and naphthalene dimer. Our results reveal that low-frequency modes dominate these dynamics, resulting primarily from intermolecular movements such as rotation and translation. Interestingly, we observed an increasing contribution of translational motion as temperature increased. Moreover, we found that coupling is sub-Ohmic in its spectral density character, with cut-off frequencies in the range of 102 cm−1. Machine-learning models allow direct study of dynamics of electronic coupling in charge transport with sufficient ensemble trajectories, providing further new insights into charge transporting dynamics. [ABSTRACT FROM AUTHOR]