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We observed a modification of transition pathways in polarized resonance Raman spectroscopy during tip-enhanced Raman spectroscopy (TERS) analysis of metallic carbon nanotubes (CNTs). At a spatial resolution reaching up to the sub-nanometer regime, the signal intensity of the typical D-band is observed to be even higher than the intensity of the G-band all over the probed CNTs in TERS imaging. The measured D-band is attributed to the non-vertical transitions of electrons in k-space that are facilitated by highly confined near-field light at the tip–sample junction of our scanning tunneling microscope based TERS system. The D-band signal was observed even when the CNTs were excited by light polarized perpendicular to the tube axis that corresponds to electronic excitations between different cutting line numbers of a CNT. By combining the electron pathways brought about by both the near-field light and its polarization, we found a unique optical transition of electrons of CNTs in near-field Raman spectroscopy. [ABSTRACT FROM AUTHOR]

A previously developed semiclassical theory of nonadiabatic energy transfer is used to analyze electronic excitation and quenching in three-dimensional atomic collisions. The predicted transition probabilities, cross sections, and rate coefficients are compared with the quantum scattering calculations for O + O and N + N, for the same interaction potentials and nonadiabatic coupling, and with the experimental data where available. The theory predictions are in very good agreement with quantum scattering, at the conditions when the energy transfer is dominated by a single pair of adiabatic potentials. Closed-form analytic expressions for the cross sections and rate coefficients are obtained, for both the strongly and weakly coupled cases. The results quantify and illustrate the effect of the interaction potentials and their coupling on the energy transfer. The analytic cross sections and rate coefficients are in good agreement with the numerical predictions. The same approach has been used to predict the rate coefficients of electronic excitation and quenching in collisions of N + O atoms. The fidelity of these predictions may be improved considerably if accurate potentials for the excited electronic states of N + O and their coupling are available. The applicability of the semiclassical theory for the prediction of the rates of heavy particle impact excitation in atom–molecule collisions is discussed. [ABSTRACT FROM AUTHOR]

We investigate how electronic excitations and subsequent dissipative dynamics in the water soluble chlorophyll-binding protein (WSCP) are connected to features in two-dimensional (2D) electronic spectra, thereby comparing results from our theoretical approach with experimental data from the literature. Our calculations rely on third-order response functions, which we derived from a second-order cumulant expansion of the dissipative dynamics involving the partial ordering prescription, assuming a fast vibrational relaxation in the potential energy surfaces of excitons. Depending on whether the WSCP complex containing a tetrameric arrangement of pigments composed of two dimers with weak excitonic coupling between them binds the chlorophyll variant Chl a or Chl b, the resulting linear absorption and circular dichroism spectra and particularly the 2D spectra exhibit substantial differences in line shapes. These differences between Chl a WSCP and Chl b WSCP cannot be explained by the slightly modified excitonic couplings within the two variants. In the case of Chl a WSCP, the assumption of equivalent dimer subunits facilitates a reproduction of substantial features from the experiment by the calculations. In contrast, for Chl b WSCP, we have to assume that the sample, in addition to Chl b dimers, contains a small but distinct fraction of chemically modified Chl b pigments. The existence of such Chl b derivates has been proposed by Pieper et al. [J. Phys. Chem. B 115, 4042 (2011)] based on low-temperature absorption and hole-burning spectroscopy. Here, we provide independent evidence. [ABSTRACT FROM AUTHOR]

A high-resolution absorption spectrum of the S1–S0 transition of free-base phthalocyanine was observed and analyzed with improved reliability. The spectrum, with a partially resolved rotational structure, was obtained by using the buffer-gas cooling technique and a single-mode tunable laser. Our new analysis reveals that the S 1 ← S 0 0 0 0 band belongs to the a-type transition, where the electronic transition moment aligns parallel to the NH–HN direction, allowing the assignment of the S1 state to 1B3u. These results agree with a prior study using supersonic expansion and are well supported by theoretical calculations. Interestingly, the rotational constant B in the S1 state, which is often smaller than that in the ground state for typical molecules, was found to be slightly larger than that in the S01Ag state. This suggests a change in the character of π bonds with the electronic excitation. [ABSTRACT FROM AUTHOR]

The photoexcitation dynamics of molecular materials on the 10–100 nm length scale depend on complex interactions between electronic and vibrational degrees of freedom, rendering exact calculations difficult or intractable. The adaptive Hierarchy of Pure States (adHOPS) is a formally exact method that leverages the locality imposed by interactions between thermal environments and electronic excitations to achieve size-invariant scaling calculations for single-excitation processes in systems described by a Frenkel–Holstein Hamiltonian. Here, we extend adHOPS to account for arbitrary couplings between thermal environments and vertical excitation energies, enabling formally exact, size-invariant calculations that involve multiple excitations or states with shared thermal environments. In addition, we introduce a low-temperature correction and an effective integration of the noise to reduce the computational expense of including ultrafast vibrational relaxation in Hierarchy of Pure States (HOPS) simulations. We present these advances in the latest version of the open-source MesoHOPS library and use MesoHOPS to characterize charge separation at a one-dimensional organic heterojunction when both the electron and hole are mobile. [ABSTRACT FROM AUTHOR]

The interaction between electrons and methane is studied with a particular focus on describing the dynamics of elastic and electronic excitation processes under the influence of the multichannel coupling effects. Elastic and electronically inelastic integral and differential cross sections are reported. These cross sections were calculated with the Schwinger multichannel method implemented with norm-conserving pseudopotentials within the minimal orbital basis for single-configuration interaction approach with up to 181 open channels. While an excellent agreement with previously published data is found in the elastic channel, the comparisons involving electronic excitation cross sections reveal significant discrepancies. Furthermore, the lack of reliable experimental data regarding the electronically inelastic channels hampers a more detailed analysis of the theoretical results. Additionally, total ionization and total cross sections for electron collisions with methane are also presented. By highlighting the current theoretical challenges in dealing with electron-induced electronic excitation of molecules, we seek to contribute to a deeper understanding of this scattering process and, thus, pave the way for future research. [ABSTRACT FROM AUTHOR]

A three-temperature collisional-radiative model for shock-heated nitrogen–argon mixtures is developed to facilitate the study of nonequilibrium electronic excitation and ionization behind strong shock waves. Model predictions accurately reproduce measurements of N 2 dissociation for mixtures of 2%–10% N 2 in argon, with some discrepancies observed for 20% N 2 mixtures. Potential causes of the discrepancies are discussed. Net dissociation in mixtures containing 20% N 2 is significantly impacted by the dissociation of N 2 (A), the first excited electronic state of N 2 , indicating that molecular electronic excitation can affect net dissociation in shock-heated nitrogen flows. The collisional-radiative model successfully predicts the three-stage behavior and induction time observed in concentration measurements of atomic nitrogen in its fourth excited state, the 3 s 4 P level, behind reflected shocks. Mechanisms for the observed behavior are discussed, which deviate from those inferred using a simpler kinetic model. Excited state number density predictions are strongly influenced by the modeling of radiation self-absorption and the inclusion of the measured non-ideal pressure rise. At higher N 2 concentrations, the measured data indicate increased efficiency of atomic nitrogen electronic excitation in collisions with N as compared to collisions with N 2 and Ar. A global sensitivity analysis of the excited state predictions is then performed, identifying the processes in the kinetic model that most sensitively influence the predicted excited state time history and further clarifying the dominant mechanisms affecting the experimental observables. [ABSTRACT FROM AUTHOR]

In this study, the total ion yield near-edge x-ray absorption fine structure spectra of four similar peptoid molecules, which differ in the numbers and positions of methyl groups, were investigated experimentally and theoretically. At each excitation energy, the intensity and branching ratio of each ionic product were measured. At a few resonant excitation energies, a specific dissociation of the C–CO bond at the nitrogen and oxygen K-edges and of the N–CO bond at the carbon K-edge was dominant, which correlated well with the predicted destination antibonding orbitals of the core electron excitation. These specific dissociation mechanisms of small peptoid molecules could provide insights into similar phenomena that occur in peptide molecules. [ABSTRACT FROM AUTHOR]

The photophysics of thiobases—nucleobases in which one or more oxygen atoms are replaced with sulfur atoms— vary greatly depending on the location of sulfonation. Not only are direct dynamics of a neutral thiobase impacted, but also the dynamics of excess electron accommodation. In this work, time-resolved photoelectron spectroscopy is used to measure binary anionic clusters of iodide and 4-thiouracil, I− · 4TU. We investigate charge transfer dynamics driven by excitation at 3.88 eV, corresponding to the lowest ππ* transition of the thiouracil, and at 4.16 eV, near the cluster vertical detachment energy. The photoexcited state dynamics are probed by photodetachment with 1.55 and 3.14 eV pulses. Excitation at 3.88 eV leads to a signal from a valence-bound ion only, indicating a charge accommodation mechanism that does not involve a dipole-bound anion as an intermediate. Excitation at 4.16 eV rapidly gives rise to dipole-bound and valence-bound ion signals, with a second rise in the valence-bound signal corresponding to the decay of the dipole-bound signal. The dynamics associated with the low energy ππ* excitation of 4-thiouracil provide a clear experimental proof for the importance of localized excitation and electron backfilling in halide–nucleobase clusters. [ABSTRACT FROM AUTHOR]

A series of (Gd, Y, Yb, Tb, Ce)3Al2Ga3O12 compositionally disordered compounds with a garnet structure were prepared in the form of ceramics by sintering in oxygen at 1650 °C for 2 h and studied for the luminescent properties and interaction of ions entering the matrix host. The luminescence features of Ce3+ ions were found to be strongly dependent on the Yb concentration. Photoluminescence and scintillation kinetics are characterized by subnanosecond kinetics when the Yb index in the compound exceeds X = 0.3. It opens an opportunity to create an extremely fast and dense scintillation material emitting in a visible range. A further decrease in the Yb index in the compound leads to an increase in the intensity of Yb3+ infrared (IR) emission, whereas Ce3+ and Tb3+ ions contribute to the luminosity of the material by overlapping intra- and intereconfiguration luminescence bands in the spectral range of 300–700 nm. This finding opens an opportunity to create converter materials tolerant to the corpuscular radiation of isotope sources, providing a high efficiency of electric current production when coupled with a silicon photovoltaic element. The compounds were engineered at the nanoscale level, providing control over electronic excitation transfer between luminescent ions. [ABSTRACT FROM AUTHOR]

This paper reports the energies and charge and spin distributions of the low-lying excited states in singlet and triplet N2V defects in diamond from direct Δ-SCF calculations based on Gaussian orbitals within the B3LYP, PBE0, and HSE06 functionals. They assign the observed absorption at 2.463 eV, first reported by Davies et al. [Proc. R. Soc. London 351, 245 (1976)], to the excitation of a N(sp3) lone-pair electron in the singlet and triplet states, respectively, with estimates of ∼1.1 eV for that of the unpaired electrons, C(sp3). In both cases, the excited states are predicted to be highly local and strongly excitonic with 81% of the C(sp3) and 87% of the N(sp3) excited charges localized at the three C atoms nearest neighbor (nn) to the excitation sites. Also reported are the higher excited gap states of both the N lone pair and C unpaired electron. Calculated excitation energies of the bonding sp3 hybrids of the C atoms nn to the four inner atoms are close to that of the bulk, which indicates that the N2V defect is largely a local defect. The present results are in broad agreement with those reported by Udvarhelyi et al. [Phys. Rev. B 96, 155211 (2017)] from plane wave HSE06 calculations, notably for the N lone pair excitation energy, for which both predict an energy of ∼2.7 eV but with a difference of ∼0.5 eV for the excitation of the unpaired electron. [ABSTRACT FROM AUTHOR]

Ultraviolet and vacuum ultraviolet photo-absorption spectra of azido (–N3)-based energetic plasticizer, bis(1,3-diazido-prop-2-yl)-malonate (abbreviated as BDAzPM), in the gas phase is recorded at room temperature and in the photon energy range of 5.5–9.9 eV using a synchrotron radiation source. Complementary computational results obtained using the time-dependent density functional theory document the vertical transition energies and oscillator strengths. Comparison of the simulated spectra with the experimental absorption spectrum of BDAzPM reveals that the early part of the absorption spectrum of BDAzPM is of pure valence excitation character, whereas the later intense part of the absorption spectrum is dominated by mixed Rydberg and valence electronic excitations. [ABSTRACT FROM AUTHOR]

The temperature dependence of the optical properties of In0.4Ga0.6As0.98N0.02 quantum dots (QDs) was investigated using continuous-wave and time-resolved photoluminescence (PL). Significant increases in the PL peak energy and the PL linewidth were observed at temperatures above 200 K, which reflected the high luminescence efficiency of ground and excited states at high temperatures. The PL decay times of the ground state were almost constant between 200 and 300 K at 200–220 ps, which were significantly longer than that of 38 ps for the In0.4Ga0.6As QDs at 300 K. The temperature independence of the PL decay time represents significant suppression of the thermal escape and the thermal excitation of electrons because the electron ground-state localization energy is much larger than the thermal energy. The PL intensity of the In0.4Ga0.6As0.98N0.02 QDs was seven times stronger than that of the In0.4Ga0.6As QDs at 300 K, and this tendency was maintained up to 400 K with a PL intensity one order of magnitude stronger. These findings demonstrate that lowering the QD conduction band by nitrogen incorporation is an effective approach for achieving strong QD luminescence above room temperature. [ABSTRACT FROM AUTHOR]

Experimental observations unambiguously reveal quasi-frictionless water flow through nanometer-scale carbon nanotubes (CNTs). Classical fluid mechanics is deemed unfit to describe this enhanced flow, and recent investigations indicated that quantum mechanics is required to interpret the extremely weak water–CNT friction. In fact, by quantum scattering, water can only release discrete energy upon excitation of electronic and phononic modes in the CNT. Here, we analyze in detail how a traveling water molecule couples to both plasmon and phonon excitations within a sub-nanometer, periodic CNT. We find that the water molecule needs to exceed a minimum speed threshold of ∼50 m/s in order to scatter against CNT electronic and vibrational modes. Below this threshold, scattering is suppressed, as in standard superfluidity mechanisms. The scattering rates, relevant for faster water molecules, are also estimated. [ABSTRACT FROM AUTHOR]

Transition state calculation is a critical technique to understand and predict versatile dynamical phenomena in solids. However, the transition state results obtained at 0 K are often utilized for the prediction or interpretation of dynamical processes at high temperatures, and the error bars of such an approximation are largely unknown. In this benchmark study, all the major temperature effects, including lattice expansion, lattice vibration, electron excitation, and band-edge shift, are evaluated with first-principles calculations for defect diffusion in solids. With the inclusion of these temperature effects, the notable discrepancies between theoretical predictions at 0 K and the experimental diffusivities at high temperatures are dramatically reduced. In particular, we find that lattice expansion and lattice vibration are the dominant factors lowering the defect formation energies and hopping barriers at high temperatures, but the electron excitation exhibits minor effects. In sharp contrast to typical assumptions, the attempt frequency with lattice expansion and vibration varies significantly with materials: several THz for aluminum bulk but surprisingly over 500 THz for 4H-SiC. For defects in semiconductors, the band-edge shift is also significant at high temperatures and plays a vital role in defect diffusion. We expect that this study would help accurately predict the dynamical processes at high temperatures. [ABSTRACT FROM AUTHOR]

We report experimental differential cross sections (DCSs) for electron impact excitation of bands I to V of benzene at incident energies of 10, 12.5, 15, and 20 eV. They are compared to calculations using the Schwinger multichannel method while accounting for up to 437 open channels. For intermediate scattering angles, the calculations reveal that the most intense band (V) emerges from surprisingly similar contributions from all its underlying states (despite some preference for the dipole-allowed transitions). They further shed light on intricate multichannel couplings between the states of bands I to V and higher-lying Rydberg states. In turn, the measurements support a vibronic coupling mechanism for excitation of bands II and IV and also show an unexpected forward peak in the spin-forbidden transition accounting for band III. Overall, there is decent agreement between theory and experiment at intermediate angles and at lower energies and in terms of the relative DCSs of the five bands. Discrepancies between the present and previous experiment regarding bands IV and V draw attention to the need of additional experimental investigations. We also report measured DCSs for vibrational excitation of combined C–H stretching modes. [ABSTRACT FROM AUTHOR]

Zirconium carbide (ZrC) is commonly used for energy sector research, as well as a surrogate for the proposed advanced nuclear fuel candidate uranium carbide. This study investigates structural modifications to nanocrystalline and microcrystalline ZrC resulting from dense electronic excitations induced by swift heavy ion exposure. Samples were irradiated with 946 MeV Au ions to various fluences up to 6 × 1013 ions cm−2 and characterized using synchrotron-based x-ray diffraction. The evolution of the unit-cell parameter and heterogeneous microstrain were evaluated as a function of fluence and compared with those of nanocrystalline and microcrystalline CeO2 (a surrogate for UO2 fuel) irradiated under identical conditions. Distinct differences were observed in the radiation responses of the carbide and oxide across both grain sizes. Most notably, microcrystalline ZrC exhibits swelling characterized by two distinct regimes, which does not result in saturation at the ion fluences achieved. This contrasts with CeO2, which exhibits the well-documented direct-impact defect accumulation mechanism, reaching a steady-state saturation of swelling at higher fluences. Nanocrystalline CeO2 undergoes more pronounced swelling compared with microcrystalline CeO2, in contrast to nanocrystalline ZrC, which exhibits only minimal unit-cell changes. These results demonstrate that swift heavy ion-induced structural changes can be quite different in carbides and oxides, which must be considered when extrapolating fission-fragment type damage in current fuels to advanced fuels. [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]

In this work, we formulate the equations of motion corresponding to the Hermitian operator method in the framework of the doubly occupied configuration interaction space. The resulting algorithms turn out to be considerably simpler than the equations provided by that method in more conventional spaces, enabling the determination of excitation energies in N-electron systems under an affordable polynomial computational cost. The implementation of this technique only requires to know the elements of low-order reduced density matrices of an N-electron reference state, which can be obtained from any approximate method. We contrast our procedure against the reduced Bardeen–Cooper–Schrieffer and Richardson–Gaudin–Kitaev integrable models, pointing out the reliability of our proposal. [ABSTRACT FROM AUTHOR]

Multiconfigurational methods (CASSCF and CASPT2) were employed to gain a new understanding of the mechanism of the gas-phase phototautomerization of 2-pyridone/2-hydroxypyridine. Potential energy curves and crossing points of the low-lying excited states were analyzed. The results show that the tautomerization only occurs from 2-pyridone to 2-hydroxypyridine after electronic excitation to the S1 (ππ*) state. From this state, the system would be able to reach a conical intersection between S1 and the dissociative S2 (πσ*) due to vibrational effects. Then, it can evolve to the hydroxy form in its ground state by reaching an intersection seam between the S0 and the πσ* states. For this to happen, a roaming process responsible for the hydrogen atom migration would be required; otherwise, the system would revert to the 2-pyridone tautomer. The unfeasibility of the reverse process after optical excitation from the lactim to the lactam form is explained by the great amount of energy needed to reach the conical intersection between the ππ* and πσ* states. These findings would provide new insights into the understanding of the photophysics and photochemistry of a primordial heterocycle, considered a prebiotic model known to be found in interstellar clouds. [ABSTRACT FROM AUTHOR]

In this article, we present a simulation study of the linear and nonlinear spectroscopy of dense atomic vapors. Motivated by recent experiments, we focus on double quantum spectroscopy, which directly probes dipole–dipole interactions. By explicitly including thermal velocity, we show that temperature has an important impact on the self-broadening mechanisms of the linear and nonlinear spectra. We also provide analytical expressions for the response functions in the short time limit using the two-body approximation, which shows that double quantum spectroscopy for atomic vapors directly probes the transition amplitude of the electronic excitation between two atoms. We also propose an expression for the double quantum spectrum that includes the effect of Doppler broadening, and we discuss the effect of density on the spectrum. We show that when Doppler broadening is negligible compared to self-broadening, the double quantum spectrum scales with the atomic density, while when Doppler broadening dominates, it scales as the square of the density. [ABSTRACT FROM AUTHOR]

Tetrathiafulvalene-p-chloranil exhibits photoinduced phase transition (PIPT) between neutral (N) and ionic (I) phases, in which the constituent molecules are approximately charge-neutral and ionic, respectively. In addition to visible-light irradiation, which can induce both N → I and I → N PIPTs, infrared irradiation has been reported to induce the N → I PIPT. These results suggest that N → I and I → N PIPTs can be driven by electronic excitation, and the I → N PIPT can also be driven by vibrational excitation. However, the feasibility of the N → I PIPT using vibrational excitation remains an open question. In this study, we address this issue by simulating the PIPT processes using a nonadiabatic molecular dynamics approach combined with real-time electron dynamics at the level of a semiempirical quantum chemical model, density-functional tight binding. The results show the importance of vibronic interactions in the PIPT processes, thereby suggesting the possibility of N → I PIPT by vibrational excitations with infrared irradiation. [ABSTRACT FROM AUTHOR]

Simulations of laser-induced electron dynamics in a molecular system are performed using time-dependent (TD) equation-of-motion (EOM) coupled-cluster (CC) theory. The target system has been chosen to highlight potential shortcomings of truncated TD-EOM-CC methods [represented in this work by TD-EOM-CC with single and double excitations (TD-EOM-CCSD)], where unphysical spectroscopic features can emerge. Specifically, we explore driven resonant electronic excitations in magnesium fluoride in the proximity of an avoided crossing. Near the avoided crossing, the CCSD similarity-transformed Hamiltonian is defective, meaning that it has complex eigenvalues, and oscillator strengths may take on negative values. When an external field is applied to drive transitions to states exhibiting these traits, unphysical dynamics are observed. For example, the stationary states that make up the time-dependent state acquire populations that can be negative, exceed one, or even complex-valued. [ABSTRACT FROM AUTHOR]

Neutron and γ-ray irradiation damages to transistors are found to be non-additive, and this is denoted as the irradiation synergistic effect (ISE). Its mechanism is not well-understood. The recent defect-based model [Song and Wei, ACS Appl. Electron. Mater. 2, 3783 (2020)] for silicon bipolar junction transistors (BJTs) achieves quantitative agreement with experiments, but its assumptions on the defect reactions are unverified. Going beyond the model requires directly representing the effect of γ-ray irradiation in first-principles calculations, which was not feasible previously. In this work, we examine the defect-based model of the ISE by developing a multiscale method for the simulation of the γ-ray irradiation, where the γ-ray-induced electronic excitations are treated explicitly in excited-state first-principles calculations. We find the calculations agree with experiments, and the effect of the γ-ray-induced excitation is significantly different from the effects of defect charge state and temperature. We propose a diffusion-based qualitative explanation of the mechanism of positive/negative ISE in NPN/PNP BJTs in the end. [ABSTRACT FROM AUTHOR]

An experimental study on the role of an external longitudinal magnetic field on the characteristics changes of pulsed plasma stream, produced in argon medium, is carried out at different time spans of its evolution. The spectroscopic observations are time integrated and are carried out at different times of plasma formation for pulsed discharge. This study gives insights into the recombination and diffusion phase of the plasma species in the presence of the magnetic field. The transition of plasma species from a dominant recombination phase to a diffusional phase is well revealed by the density profile during the time evolution. Moreover, the decrease in electron temperature and the increase in electron excitation temperature explain the energy transfer to electrons due to metastable quenching, and the system gradually approaches equilibrium. The magnetic field also affects the transitions of the ionized argon population between different energy levels. It is found that faster decay occurs for transitions of different plasma species to non-metastable states, while the populations of metastable states exist for a longer time. In addition, the time-resolved morphology changes of the plasma stream are also observed by high speed imaging, which shows the flow structure of the plasma stream at different time frames. The imaging of the plasma stream evolution shows the initial ejection of the plasma sheet from the electrode assembly, its detachment, the steady flow, and gradually its nature of dying out. [ABSTRACT FROM AUTHOR]

In purple bacteria, the fundamental charge-separation step that drives the conversion of radiation energy into chemical energy proceeds along one branch—the A branch—of a heterodimeric pigment–protein complex, the reaction center. Here, we use first principles time-dependent density functional theory (TDDFT) with an optimally-tuned range-separated hybrid functional to investigate the electronic and excited-state structure of the six primary pigments in the reaction center of Rhodobacter sphaeroides. By explicitly including amino-acid residues surrounding these six pigments in our TDDFT calculations, we systematically study the effect of the protein environment on energy and charge-transfer excitations. Our calculations show that a forward charge transfer into the A branch is significantly lower in energy than the first charge transfer into the B branch, in agreement with the unidirectional charge transfer observed experimentally. We further show that the inclusion of the protein environment redshifts this excitation significantly, allowing for energy transfer from the coupled Qx excitations. Through analysis of transition and difference densities, we demonstrate that most of the Q-band excitations are strongly delocalized over several pigments and that both their spatial delocalization and charge-transfer character determine how strongly affected they are by thermally-activated molecular vibrations. Our results suggest a mechanism for charge-transfer in this bacterial reaction center and pave the way for further first-principles investigations of the interplay between delocalized excited states, vibronic coupling, and the role of the protein environment in this and other complex light-harvesting systems. [ABSTRACT FROM AUTHOR]

We have conducted time-resolved experiments (pump–probe and pump–repump–probe) on a model aromatic chromophore, aniline, after excitation in water at 267 nm. In the initial spectra recorded, in addition to the absorption corresponding to the bright ππ* excitation, the fingerprint of a transient state with the electron located on the solvent molecule is identified. We postulate that the latter corresponds to the πσ* state along the N–H bond, whose complete relaxation with a ∼500 ps lifetime results in the formation of the fully solvated electron and cation. This ionization process occurs in parallel with the ππ* photophysical channel that yields the characteristic ∼1 ns fluorescence lifetime. The observed branched pathway is rationalized in terms of the different H-bonds that the water establishes with the amino group. The proposed mechanism could be common for aromatics in water containing N–H or O–H bonds and would allow the formation of separated charges after excitation at the threshold of their electronic absorptions. [ABSTRACT FROM AUTHOR]

Slow (meV) photoelectron imaging spectroscopy is employed in the experimental study of near-threshold photoionization of strontium atoms in the presence of an external static electric field. Specifically, the study is devoted to the glory effect, that is, the appearance of an intense peak at the center of the recorded photoelectron images, when dealing with m = 0 final ionized Stark states (m denoting the magnetic quantum number). This critical effect is formally identical to that encountered in classical scattering theory, where, for a nonzero value of the impact parameter, the zero-crossing of the deflection function leads to a divergent classical differential cross section. By recording the magnitude variation of this glory peak as a function of electron excitation energy, we observe that, besides the traces of classical origin, it also exhibits intense quantum interference and beating phenomena, above and below the zero-static-field ionization threshold. We study both, single- and two-photon ionization of Sr, thus enabling a comparison not only between the different excitation schemes, but also with an earlier work devoted to two-photon ionization of Mg atom by Kalaitzis et al (2020 Phys. Rev. A 102 033101). Our recordings are analyzed within the framework of the Harmin–Fano frame transformation Stark effect theory that is applied to both the hydrogen atom and a non-hydrogenic one simulating Sr. We discuss the various aspects of the recorded and calculated glory interference and beating structures and their 'short time Fourier transforms' and classify them as either atom-specific or atom independent. In particular, we verify the 'universal' connection between the glory oscillations above the zero-field threshold and the differences between the origin-to-detector times of flight corresponding to pairs of classical electron trajectories that end up to the image center. [ABSTRACT FROM AUTHOR]

The electronic excitations of conformationally constrained bithiophene cage systems as previously investigated by Lewis et al. (J. Am. Chem. Soc. 143, 18548 (2021)) are revisited, employing the correlated ab initio Scaled Opposite‐Spin Algebraic Diagrammatic Construction Second Order electronic structure method. Quantitative descriptors are determined to assess the extent of charge transfer between the bithiophene moieties and the capping domains, represented by either phenyl or triazine groups. The investigation substantiates intrinsic differences in the photophysical behavior of these two structural variants and reveals the presence of lower‐energy excited states characterized by noteworthy charge transfer contributions in the triazine cage system. The manifestation of this charge transfer character is discernible even at the Franck–Condon geometry, persisting throughout the relaxation of the excited state. By examining isolated monomer building blocks, we confirm the existence of analogous charge transfer contributions in their excitations. Employing this methodological approach facilitates the prospective identification of potential wall/cap chromophore pairs, wherein charge transfer pathways can be accessed within the energetically favorable regime. [ABSTRACT FROM AUTHOR]

Large-scale plumes in a plasma jet are desirable for fast processing of materials with large surface, which are normally composed of discharge filaments. A filamentary plume may cause nonuniform treatment or even damage to vulnerable samples. In this Letter, an argon plasma jet in a gas-confined barrier discharge geometry is proposed to generate a large-scale filament-free plume. Results indicate that the filament-free plume can only be sustained in a relatively low voltage amplitude (Vp), which transits to the filamentary plume with increasing Vp. There is only one negative discharge per voltage cycle for the filament-free plume, while both positive and negative discharges for the filamentary plume. Fast photography reveals that the negative discharge is diffuse, originating from the propagation of a negative streamer. On the contrary, the positive discharges are filamentary. Optical emission spectroscopy indicates that the filament-free plume has lower electron density, electron excitation temperature, and molecular vibrational temperature compared to the filamentary plume, while gas temperature keeps at a low value with varying Vp. [ABSTRACT FROM AUTHOR]

In this study, the photoluminescence (PL) behavior of two aluminosilicate glass series containing alkali-niobates ranging from 0.4 to 20 mol% was investigated. The glasses exhibit an intense visible emission centered at ~18,400 cm−1 for the peralkaline series and at higher energies (~19,300 cm−1) for the metaluminous glasses. However, the photoluminescence emission intensity varies significantly with the niobate content and the bulk chemistry. PL and fluorescence lifetime measurements indicate that the broad emission bands result from the overlap of different niobate populations, whose distribution changes with niobate content. The distinct PL behavior in the two glass series was related to the structural evolution of the niobate units upon niobium addition. An enhancement of the visible emission was observed for a higher fraction of distorted [NbO6] units. Eu-doping was carried out as a structural probe of the glass network, and also to determine if these glasses could be used as potential rare earth element (REE) activators. The crystal field strength around Eu ions is strongly dependent on the bulk chemistry and the niobate content. Furthermore, the peralkaline series showed energy transfer from the host [NbO6] to Eu3+, confirming the feasibility of exploring niobate glasses and glass-ceramics as lanthanide ion-activated luminescent materials. In addition, glass-ceramics (GCs) containing alkali-niobate phases with a perovskite-like structure were developed and studied to verify the optical performance of these materials. It was verified that the bulk chemistry influences crystallization behavior, and also the photoluminescence response. The transparent GC from the metaluminous series exhibits a quenching of the Eu3+ emission, whereas an enhanced emission intensity is observed for the peralkaline GC. The latter shows a strong excitation-dependent PL emission, suggesting energy transfer and migration of electronic excitation from one Eu population to another. Additionally, Eu3+ emissions arising from the D 1 5 and D 2 5 excited states were observed, highlighting the low phonon energy achievable in niobo-aluminosilicate hosts. [ABSTRACT FROM AUTHOR]

Both microvoids and helium (He) impurities are widely present in tungsten (W) plasma-facing materials (PFMs), where the interaction between microvoids and He atoms has led to the intriguing development of microvoids. In this paper, we comprehensively investigated the interaction between He atoms and trivacancy (V3), a fundamental microvoid in W-PFMs, at the level of tight-binding theory. Our study showed that He atoms can catalyze the decomposition of the original V3 or facilitate its transformation into another V3 variant. We propose that a He atom near the V3 defect induces significant changes in the distribution of d-electron charges within the W atoms lining the inner wall of the V3 defect, making the W atom nearest to this He atom cationic and the other W atoms anionic. The attractive interaction between them promotes the decomposition and deformation of V3. As electronic excitation increases, the ionization of W atoms on the V3 wall gradually intensifies, thereby enhancing the cationic characteristics of the W atoms closest to the He atom. This process also prompts other W atoms to shift from anions to cations, leading to a transition in the electrostatic interactions between them from attraction to repulsion. This transformation, driven by electronic excitation, plays a significant inhibitory role in the decomposition and deformation of V3. [ABSTRACT FROM AUTHOR]

Solar-driven interfacial evaporation technology has great potential in solving the global challenge of freshwater shortage. However, the selection of excellent photothermal conversion materials is a challenging task. To achieve efficient solar interface evaporation materials, we developed a new material loaded with Fe/Fe3C nanoparticles on mesoporous carbon hollow spheres (MCHSs). As an interfacial evaporation material, Fe/Fe3C@MCHS-x has an evaporation rate of 1.633 kg m−2 h−1 and an energy conversion efficiency of 94.17% (Fe/Fe3C@MCHS-2). The innovative introduction of magnetic particles into the evaporation unit allows the metal nanoparticles to absorb light at their resonance wavelength. This absorption leads to the excitation of electrons from the occupied state to the unoccupied state, and the diffusion of thermoelectrons leads to an increase of carriers, which makes the interface temperature rise rapidly. The composite material has a certain degree of organic pollution treatment capability along with high-efficiency water evaporation, which provides new ideas for interfacial evaporation material technology. [ABSTRACT FROM AUTHOR]

Conventional quantum-mechanical calculations of molecular properties, such as dipole moments and electronic excitation energies, give errors that depend linearly on the error in the wave function. An exception is the electronic energy, whose error depends quadratically on the error in wave function. We here describe how all properties may be calculated with a quadratic error, by setting up a variational Lagrangian for the property of interest. Because the construction of the Lagrangian is less expensive than the calculation of the wave function, this approach substantially improves the accuracy of quantum-chemical calculations without increasing cost. As illustrated for excitation energies, this approach enables the accurate calculation of molecular properties for larger systems, with a short time-to-solution and in a manner well suited for modern computer architectures. [ABSTRACT FROM AUTHOR]

A change of orbital state alters the coupling between ions and their surroundings drastically. Orbital excitations are hence key to understand and control interaction of ions. Rare-earth elements with strong magneto-crystalline anisotropy (MCA) are important ingredients for magnetic devices. Thus, control of their localized 4f magnetic moments and anisotropy is one major challenge in ultrafast spin physics. With time-resolved x-ray absorption and resonant inelastic scattering experiments, we show for Tb metal that 4f-electronic excitations out of the ground-state multiplet occur after optical pumping. These excitations are driven by inelastic 5d-4f-electron scattering, altering the 4f-orbital state and consequently the MCA with important implications for magnetization dynamics in 4f-metals and more general for the excitation of localized electronic states in correlated materials. [ABSTRACT FROM AUTHOR]

With the development of wearable and wireless electronic devices, the triboelectric nanogenerator (TENG) is attracting interest as a candidate for portable power. Many studies are conducted to increase the surface charge density of the TENG, such as external charge pumping or external electron excitation strategies. However, there are limitations in that another additional external energy source is required. Here, a TENG–capacitor (TC) coupling system that can maximize energy generation and storage efficiency within a limited volume is proposed. Density functional theory calculations indicate that the electric field induced on capacitor increases the fermi energy of positive triboelectric material, resulting in more charge transfer between two triboelectric materials. TC coupling system enhances TENG output performance and the capacitor charging rate in a virtuous cycle. This study provides new insights into TENG structural design and an important guideline for the use of TENG as a portable power source for wearable and wireless applications. [ABSTRACT FROM AUTHOR]

Er3+‐doped polycrystalline MgAl2O4 (MAO:Er) spinel nanofilms are deposited via atomic layer deposition, and the metal‐oxide–semiconductor light emitting devices are fabricated. The crystallinity and morphology of the MAO:Er nanofilms are explored by modifying the annealing temperatures, Al2O3/MgO ratios and Er2O3 dopant cycles. The similar electroluminescence (EL) emissions peaking at 1530 nm indicates the identical crystal field environment for the doped Er3+ ions. The concentration quenching is verified to occurs via the energy transfer among the neighboring Er3+ ions. The optimal device (800 °C‐annealed, Al2O3/MgO ratio close to stoichiometry, Er3+: 1.85 mol%) yields the highest external quantum efficiency of 28%, the power efficiency of 0.32% and the optical power density of 14.62 mW cm−2. The smooth MAO:Er spinel nanofilms with the low refractive index and high resistance ensure the highly efficient light extraction and the generation of energetic electrons for the impact excitation of Er3+ ions. The trap‐assisted tunneling under operation electric field dominates the conduction mechanism for the EL emissions. The estimated decay lifetime of 1154.4 µs and a large‐stimulated emission cross‐section in the order of 10−15–10−14 cm2 are revealed from the EL emissions. Intense near‐infrared emissions from these Si‐based MAO:Er devices have great potential in the optoelectronic applications. [ABSTRACT FROM AUTHOR]

Raman spectroscopy together with density functional calculations were used to study lattice dynamics in a layered honeycomb cobaltite Na3Co2SbO6, which can host a field-induced phase related with the Kitaev physics. We show that there develops an additional mode well above Neel temperature (at K) at 525 cm–1, which origin can be related to electronic excitation to one of doublets. Moreover, our theoretical calculations demonstrate that the highest frequency intensive mode related to the oxygen vibrations is very sensitive to type of the magnetic order. Thus, we propose to use the softening of this mode as a hallmark of the transition to a fully polarized regime, which is stabilized in Kitaev materials in strong magnetic fields. [ABSTRACT FROM AUTHOR]

The structure of dislocation cores, the fundamental knowledge on crystal plasticity, remains largely unexplored in covalent crystals. Here, we conducted atomically resolved characterizations of dislocation core structures in a plastically deformed diamond anvil cell tip that was unloaded from an exceptionally high pressure of 360 GPa. Our observations unveiled a series of nonequilibrium dislocation cores that deviate from the commonly accepted "five-seven-membered ring" dislocation core model found in FCC-structured covalent crystals. The nonequilibrium dislocation cores were generated through a process known as "mechanical quenching," analogous to the quenching process where a high-energy state is rapidly frozen. The density functional theory-based molecular dynamic simulations reveal that the phenomenon of mechanical quenching in diamond arises from the challenging relaxation of the nonequilibrium configuration, necessitating a large critical strain of 25% that is difficult to maintain. Further electronic-scale analysis suggested that such large critical strain is spent on the excitation of valance electrons for bond breaking and rebonding during relaxation. These findings establish a foundation for the plasticity theory of covalent materials and provide insights into the design of electrical and luminescent properties in diamond, which are intimately linked to the dislocation core structure. [ABSTRACT FROM AUTHOR]

Laser Wakefield Acceleration (LWFA) has emerged as a groundbreaking approach for generating ultra-high energy electron beams over short distances, revolutionizing the field of particle acceleration. In this paper, we investigate the novel concept of employing sin-Gaussian laser pulse for enhanced LWFA performance. sin-Gaussian pulses combine the advantageous features of both sinusoidal and Gaussian pulse shapes, offering unique opportunities for generating the plasma wakefield and optimizing electron acceleration. We present a comprehensive theoretical analysis of the interaction between a sin-Gaussian laser pulse and an underdense plasma medium, elucidating the intricate dynamics of the wakefield excitation and electron acceleration. Through analytical study, we demonstrate that the sin-Gaussian pulse configuration leads to a significant energy gain (Maximum gain of 2.06 GeV with chosen parameters) for plasma electrons. Furthermore, we explore the effects of varying key parameters such as the laser electric field amplitude and beam waist on the acceleration performance. Our findings reveal the underlying physics governing the interplay between these parameters and the resulting electron energy spectra for LWFA outcomes. [ABSTRACT FROM AUTHOR]

The modern means of controlled irradiation by femtosecond lasers or swift heavy ion beams can transiently produce such energy densities in samples that reach collective electronic excitation levels of the warm dense matter state, where the potential energy of interaction of the particles is comparable to their kinetic energies (temperatures of a few eV). Such massive electronic excitation severely alters the interatomic potentials, producing unusual nonequilibrium states of matter and different chemistry. We employ density functional theory and tight binding molecular dynamics formalisms to study the response of bulk water to ultrafast excitation of its electrons. After a certain threshold electronic temperature, the water becomes electronically conducting via the collapse of its bandgap. At high doses, it is accompanied by nonthermal acceleration of ions to a temperature of a few thousand Kelvins within sub-100 fs timescales. We identify the interplay of this nonthermal mechanism with the electron–ion coupling, enhancing the electron-to-ions energy transfer. Various chemically active fragments are formed from the disintegrating water molecules, depending on the deposited dose. [ABSTRACT FROM AUTHOR]

As the Cantor-derived medium-entropy alloys (MEAs), FeNiCoMn and FeNiCrMn quaternaries in both equiatomic and non-equiatomic compositions were investigated by density functional theory combined with the quasiharmonic Debye–Grüneisen approximation using the special-quasirandom structure model. The structural properties, magnetic properties, and thermodynamics and phase stability were explored in detail. The temperature stabilization effect of lattice vibration, configurational mixing entropy, and thermal electronic excitation was discussed. Also FeNiCoPd and FeNiCrPd quaternaries, in which Mn was replaced by Pd, were considered in the same framework in order to highlight the similarities and differences between these Mn- and Pd-MEAs. The phase stability competition between homogeneous and inhomogeneous states in terms of both size and chemical ordering was revealed for four groups of FeNiCoMn, FeNiCoPd, FeNiCrMn, and FeNiCrPd MEAs. [ABSTRACT FROM AUTHOR]

A comprehensive investigation of elastic and inelastic electron scattering from molecular pyridine is reported using the ab initio R-matrix method with the static exchange plus polarization and close-coupling approximations for incident energies up to 10 eV. The two well-known low-lying 1 2B1 and 1 2A2 shape resonances as well as a 2 2B1 mixed-character resonance compare well with the theoretical and experimental results. We also detect five core-excited resonances (1 2A1, 1 2B2, 3 2B1, 2 2A2, and 4 2B1), which lie above the first electronic excitation threshold. The total elastic cross sections and momentum transfer cross sections agree reasonably with previous reference data. Comparisons of the differential elastic cross sections of pyridine with those measured for benzene, pyrazine, and pyrimidine show remarkable agreement at scattering angles above 40° but behave differently for forward scattering below 40° below 6 eV, due to the dominant effect of the permanent dipole moment on the differential cross section in the low energy region with narrow scattering angles. Inelastic electronic excitation cross sections are presented, showing the influence of core-excited resonances below the ionization threshold for the first time. [ABSTRACT FROM AUTHOR]

C4F7N is a promising candidate for the replacement of sulfur hexafluoride as an insulating medium, and it is important to understand the chemical changes initiated in the molecule by collision with free electrons, specifically the formation of neutral fragments. The first step of neutral fragmentation is electronic excitation, yet neither the absorption spectrum in the vacuum ultraviolet (VUV) region nor the electron energy loss spectrum have previously been reported. Here, we experimentally probed the excited states by VUV photoabsorption spectroscopy and electron energy loss spectroscopy (EELS). We found that the distribution of states populated upon electron impact with low-energy electrons is significantly different from that following photoabsorption. This difference was confirmed and interpreted with ab initio modeling of both VUV and EELS spectra. We propose here a new computational protocol for the simulation of EELS spectra combining the Born approximation with approximate forms of correlated wave functions, which allows us to calculate the (usually very expensive) scattering cross sections at a cost similar to the calculation of oscillator strengths. Finally, we perform semi-classical non-adiabatic dynamics simulations to investigate the possible neutral fragments of the molecule formed through electron-induced neutral dissociation. We show that the product distribution is highly non-statistical. [ABSTRACT FROM AUTHOR]

Coherent anti-Stokes Raman Scattering (CARS) spectroscopy is a nonlinear optical technique that is used to investigate many different chemical and biological systems. This tool is very efficient and essentially completely rejects fluorescence. As is well known, the excitation profiles of resonance CARS are mostly used to estimate the origin shift parameters with electronic excitation for vibrations with resonantly enhanced Raman components that give information about the molecular structure and its changes in an excited electronic state. Certainly, it is necessary to have an appropriate theoretical model for pragmatically representing these processes and considering the joint (simultaneous) impact of different broadening mechanisms. The theoretical model presented in the paper is the most general and is free from a priori assumptions. Also, the mathematical algorithm created on its basis is flexible and fast for quantitative calculations. [ABSTRACT FROM AUTHOR]

To assign cis and trans isomers of m-tolyl isocyanate (mTI) and p-phenylene diisocyanate (pPDI) in the electronic excitation transition, we measured the time-of-flight mass-selected resonant ionization spectra of jet-cooled phenyl isocyanate (PI), mTI, and pPDI in the region of the 275 nm first ππ* absorption system. In the excitation spectra of jet-cooled mTI and pPDI, cis- and trans-rotational isomers appeared as doublets. Isomers were assigned by analyzing the methyl-group internal rotation for mTI and by applying low-frequency bending vibrations to the mutual exclusion rule between the one- and two-photon spectra for pPDI. The electronic spectra of the three molecules observed in the jet were assigned to the transition to the first ππ* and third singlet excited states with the aid of time-dependent (TD)-B3LYP/aug-cc-pVDZ and TD-CAM-B3LYP/aug-cc-pVDZ calculations. The 0 − 0 band of PI was observed at 36 354 cm−1, those of the cis and trans isomers of mTI at 36 018 and 35 853 cm−1, respectively, and those of the cis and trans isomers of pPDI at 34 437 and 34 383 cm−1, respectively. All vibronic bands were diffuse, probably because of internal conversion to two singlet nπ* states. For mTI, based on changes in the barrier height of methyl-group internal rotation upon excitation, the Hammett-σm of PI was determined to be −0.12. [ABSTRACT FROM AUTHOR]

Pyrene fluorescence after a high-energy electronic excitation exhibits a prominent band shoulder not present after excitation at low energies. The standard assignment of this shoulder as a non-Kasha emission from the second-excited state (S2) has been recently questioned. To elucidate this issue, we simulated the fluorescence of pyrene using two different theoretical approaches based on vertical convolution and nonadiabatic dynamics with nuclear ensembles. To conduct the necessary nonadiabatic dynamics simulations with high-lying electronic states and deal with fluorescence timescales of about 100 ns of this large molecule, we developed new computational protocols. The results from both approaches confirm that the band shoulder is, in fact, due to S2 emission. We show that the non-Kasha behavior is a dynamic-equilibrium effect not caused by a metastable S2 minimum. However, it requires considerable vibrational energy, which can only be achieved in collisionless regimes after transitions into highly excited states. This strict condition explains why the S2 emission was not observed in some experiments. [ABSTRACT FROM AUTHOR]

Optimizing the performance of semiconductors in both classical and quantum applications, not only requires a solid understanding of elementary excitations such as electrons, holes, or bound electron–hole pairs (excitons), but also of their interaction with the host material's vibrational states (phonons). Exciton‐phonon coupling is particularly relevant in quantum dots (QDs) of APbX3 lead‐halide perovskite (where "A" can be Cs, formamidinium (FA), or methylammonium (MA), and X can be Cl, Br, or I), a new class of semiconductors with a soft crystal structure. Here, they quantify the strength of coupling to interband transitions for both FAPbBr3 and CsPbBr3 QDs, via the magnitude of phonon replicas in their photoluminescence (PL) spectra at cryogenic temperatures. CsPbBr3 QDs exhibit weaker exciton‐phonon coupling than similarly sized FAPbBr3 QDs. While the phonon energies are size‐independent, the exciton‐phonon coupling strength decreases with increasing QD size due to the decreased coupling of the transition to low‐energy surface‐enhanced phonon modes, consistent withab initio molecular‐dynamics (AIMD) simulations. Furthermore, within the harmonic approximation, the size‐dependent PL linewidth at room temperature can coarsely be estimated from the low‐temperature phonon replica spectrum, highlighting the crucial role of anharmonic effects. These findings contribute to realizing perovskite QD‐based devices with narrow and coherent emission for quantum technologies. [ABSTRACT FROM AUTHOR]

In this research, we use the dual lengthscale quasiparticle model for collective quantum excitations in electron gas to study the time evolution of the Wigner function. The linearized time-dependent Schrödinger–Poisson system for quasiparticles is used to study the dynamics of initial known stationary and damped solutions in an electron gas with arbitrary degree of degeneracy. The self-consistent potential in the Schrödinger–Poisson model is treated in a quite different manner in this analysis due to the effective coupling of the electrostatic field to the electron density, which leads to a modified Wigner function. It is shown that the modified Wigner function in the absence of external potential evolves similar to the system of free particles, a feature of collective quantum excitations which is quite analogous to freely evolving classical system of particles in the center of mass frame in the absence of external forces. The time evolution of the modified Wigner function reveals a grinding effect on large-amplitude density structures present at initial states, which is a characteristic feature of the Landau damping in plasmas. It is further shown that linear phase-space dynamics of spill-out electrons (damped quasiparticles) can be described similar to free quasiparticles with imaginary momentum. The later predicts the surface electron tunneling via the collective excitations of spill-out electrons at the half-space boundary, which is closely related to the Heisenberg's uncertainty principle. Current research can have applications in plasmonics and related fields. [ABSTRACT FROM AUTHOR]