Electronic Excitation Research Articles

Quantum theory of the spin dynamics excited by ultrashort THz laser pulses in rare earth antiferromagnets. DyFeO3

A quantum theory of spin dynamics in the rare-earth orthoferrites excited by terahertz laser pulses is developed. The study demonstrates that dynamic magnetic configurations, triggered by a light pulse, exhibit stability even after the excitation source is ceased. The magnitude of post-excitation oscillations is linked to the ratio between the frequency of rare-earth ion excitations and the frequency of the external source. According to the analysis presented, dynamic response is significantly amplified when the system is exposed to ultrashort terahertz pulses. The physical characteristics of the oscillations emerging after the pulse are determined, and the factors governing their amplitude and phase are identified. The response signal is found to be dependent on the initial part of the pulse, specifically the half-period of the ultrashort light wave, while the subsequent part of the pulse contributes minimally to post-pulse magnetization dynamics. The findings highlight that in DyFeO3, terahertz dynamics primarily result from the influence of the magnetic field of the light, leading to excitations of electrons from the ground state to low-lying electronic levels of Dy3+ions. Additionally, the dynamic magnetoelectric effect excited by the electric field of the pulse is explored, revealing the emergence of odd magnetic modes.

A procedure for the visualization of fingerprint traces on standard and thermal paper using the electron excitation energy of 1,8-diazafluoren-9-one aggregates in a polyvinylpyrrolidone polymer

A procedure for the visualization of fingerprint traces on standard and thermal paper using the electron excitation energy of 1,8-diazafluoren-9-one aggregates in a polyvinylpyrrolidone polymer

Abnormal Relaxation Behavior of Excited Electrons in the Flat Band of Kagome Compound Nb3Cl8.

Carrier dynamics is crucial in semiconductors, and it determines their conductivity, response time, and overall functionality. In flat bands (FBs), carriers with high effective masses are predicted to host unconventional transport properties. The FBs usually overlap with other trivial energy bands, however, making it difficult to accurately distinguish their carrier dynamics. In this paper, we have investigated the flat-band carrier dynamics of excited electrons in Nb3Cl8, which hosts ideal nonoverlapping FBs near the Fermi level. The optical transition between Hubbard bands is abnormally weakened, exhibiting weak interband absorption and its related slow photoresponse with a time constant of ∼120 s, which are associated with flat-band Mottness-induced large electron effective mass and parity-forbidden transitions. Besides, the localized states created by chlorine vacancies also act as trapping centers for carriers with a time constant of ∼600 s, which are similar to those of the compact localized states of the FB, making the relaxation behavior even more extraordinary. The presence and impacts of atomic defects are confirmed experimentally and theoretically. This work has revealed the abnormal flat-band carrier dynamics of Nb3Cl8, which is essential for understanding the optical, electrical, and thermal transport properties of flat-band materials.

МЕТОД ТА ДОСЛІДЖЕННЯ ТОЧНОСТІ ОБЧИСЛЮВАННЯ МАТЕМАТИЧНОЇ МОДЕЛІ ЕЛЕКТРОГІДРАВЛІЧНОГО ЕФЕКТУ

The mathematical model of the electrohydraulic effect (EHE) is a nonlinear non-stationary system of partial differential equations (PDE), which reflects the motion and contact interaction of two media, gaseous and liquid, under the action of pulsed thermal excitation. Such PDE systems generally do not have analytical solutions and are solved only by numerical methods, which are approximate in nature, i.e. they provide a solution with some error. The peculiarity of the motion of media in the case of EHE is large deformations in the form of flows and vortices. This feature imposes significant restrictions on the choice of the method for solving the PDE model. The widely known Lagrangian finite element method used to solve contact problems, in the case of EHE modeling leads to a pathological change in the shape of the finite elements, and therefore to instability of the calculation process and an unlimited increase in error. In calculation practice, a variant of the finite element method, FEM-ALE, has become widespread. It uses both Lagrangian and Eulerian grids of nodes and a special advection procedure, i.e., transfer by interpolation of the solution from the Lagrangian grid to the Eulerian one, and then vice versa from the Eulerian one to another new Lagrangian grid. Such an additional interpolation procedure, which is used repeatedly in the calculation, leads to additional (in comparison with the Lagrangian FEM) errors. If the causes and kinetics, as well as the methods of error control in the case of the Lagrangian FEM, have been sufficiently studied in the literature, then the kinetics of error development in the simulation of the EGE using the FEM-ALE method has been practically not studied. The article is devoted to the study of the development of errors in the numerical solution in this particular case. An analytical solution of the problem in the asymptotic case for a technological system with a rigid chamber is obtained. This solution is analyzed in comparison with the numerical solution using the FEM-ALE method. Conclusions are made regarding the errors in calculating pressure as the main factor of mechanical impact of EGE on the technological object and technological equipment, as well as errors in calculating deformations of gaseous and liquid media.The scientific novelty consists in the development of a method for determining the accuracy of EHE parameter calculations using the MSE-ALE method. The practical value lies in determining the accuracy of calculating the parameters of the EHE mathematical model, which makes it possible to justify the use of numerical modeling as a method of researching technological processes and systems using EHE

Intracage vibrations and Zeeman effect in Y3N@C80 single-molecule transistors

Clusterfullerenes, which contain a cluster rather than single-atom inclusions, exhibit more complex internal structures and greater degrees of freedom for motion. Trimetallic nitride clusterfullerenes have attracted significant attention due to their diversity and potential applications, among which Y3N@C80 stands out for its charge-transfer characteristics in electronic excitations, owing to the unique distribution of molecular orbitals near the Fermi level. Here, we have fabricated single-molecule transistor devices using Y3N@C80. Transport measurements at liquid helium temperature revealed a series of excited state energy levels, which were matched to corresponding vibrational modes through comparison with Raman spectra and density functional theory calculations. Additionally, we measured charge-state-dependent magnetic responses, revealing the electron and spin-filling patterns of the molecular orbitals in Y3N@C80. These results enhance our understanding of the dynamics and molecular spin–orbit characteristics of clusterfullerenes, indicating their potential for multifunctional applications.

Comparison of Matrix Product State and Multiconfiguration Time-Dependent Hartree Methods for Nonadiabatic Dynamics of Exciton Dissociation.

The excited-state dynamics of organic molecules, molecular aggregates, and donor-acceptor clusters is typically governed by the interplay of electronic excitations and, due to their flexibility and soft bonding, by the interaction with their vibrations. This interaction in these systems can be characterized by a few relevant electronic states that are coupled to numerous vibrational normal modes, encompassing a vast configurational space of the molecules. The full quantum simulation of these type of systems has been long dominated by the multiconfiguration time-dependent Hartree (MCTDH) approach and its multilayer variants, which are considered the gold standard in the presence of electron-vibration coupling with a large number of modes. Recently, also the matrix product state ansatz (MPS) with appropriate time-evolution schemes has been applied to these types of Hamiltonians. In this article, we provide a numerical comparison of excited-state dynamics between the MCTDH and MPS approaches for two electron-vibration coupled systems. Notably, we consider two models for exciton dissociation at a P3HT:PCBM heterojunction, comprising two electronic states and 100 vibrational modes, and 26 electronic states and 113 vibrational modes, respectively. While both methods agree very well for the first model, more pronounced deviations are found for the second model. We trace back the divergence between the methods to the different way entanglement is treated.

Insights into Ultrafast Relaxation Dynamics of Electronically Excited Furfural and 5-Methylfurfural.

The ultrafast relaxation dynamics of furfural and 5-methylfurfural following excitation in the ultraviolet range is investigated using the femtosecond time-resolved photoelectron spectroscopy method. Specifically, the pump wavelength-dependent decay dynamics of electronically excited furfural and 5-methylfurfural is discussed on the basis of a detailed analysis of our measured time-resolved photoelectron spectroscopy spectra. Irradiation at all pump wavelengths prepares both furfural and 5-methylfurfural molecules with different vibrational levels in the first optically bright S2 (1ππ*) state, the lifetime of which is measured to be at least hundreds of femtoseconds. Besides the prominent deactivation channels of ring-opening and ring-puckering pathways for the S2(1ππ*) state, we propose that there is a minor decay channel of internal conversion from the initially prepared S2(1ππ*) state to the S1(1nπ*) state. The wavepacket decays out of the Franck-Condon region on the S2(1ππ*) state potential energy surface and bifurcates into different parts somewhere. A small fraction of the wavepacket funnels down to the S1(1nπ*) state via internal conversion. The subsequently populated S1(1nπ*) state contains large vibrational excess energy and decays over a lifetime of 2.5-2.8 ps. One of the deactivation channels of the S1(1nπ*) state is intersystem crossing to the 3ππ* triplet state. In addition, methyl substitution effects on the excited-state dynamics of furfural are also discussed. This experimental study provides new insights into the excitation energy-dependent decay dynamics of photoexcited furfural and 5-methylfurfural.

Nonlinear scintillation effects in the intrinsic luminescence from Sc1.318Y0.655Si1.013O4.987 crystal excited by electrons and γ-quanta

The spectral and kinetic properties of intrinsic luminescence from (Y2Sc1)0.(3)(Sc)[Si]O5 crystal are studied. The emission is excited by electrons and γ-quanta. The composition (Y2Sc1)0.(3)(Sc)[Si]O5 is the congruent one for Sc2SiO5-Y2SiO5 solid solutions. It is found, that the crystal emits fairly bright intrinsic cathodololuminescence (CL) and radioluminescence (RL) at room temperature. In particular, the light yield of scintillation excited by γ-quanta with the energies of 661.7 keV is of 12000 photons/MeV. An increase in the beam flux by ∼20 times leads to the shift in the maximal CL energy spectral density from 315 to 340 nm and to the decrease in the CL decay time at 415 nm from 1377 ± 3 ns to 1165 ± 1 ns. Simultaneously, the decay time of RL excited by a photoelectron with the energy of 644.7 keV is of 1310 ± 10 ns while a Compton electron with the energy of 477 keV excites RL with the decay time of 1050 ± 10 ns. Also, we observed differences in the CL yield dependencies on the volume-averaged density of electronic excitations (EEs) at different wavelengths. An explanation of the results is given considering the nonlinear scintillation phenomena induced by an interaction between EEs. It is based on a conception that an increase in EE volume density leads to an increase in EEs nonradiative quenching due to these interactions.

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

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

Anisole-Water and Anisole-Ammonia Complexes in Ground and Excited (S1) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study.

Binary complexes of anisole have long been considered paradigm systems for studying microsolvation in both the ground and electronically excited states. We report a symmetry-adapted perturbation theory (SAPT) analysis of intermolecular interactions in anisole-water and anisole-ammonia complexes within the framework of the multireference SAPT(CAS) method. Upon the S1 ← S0 electronic transition, the hydrogen bond in the anisole-water dimer is weakened, which SAPT(CAS) shows to be determined by changes in the electrostatic energy. As a result, the water complex becomes less stable in the relaxed S1 state despite decreased Pauli repulsion. Stronger binding of the anisole-ammonia complex following electronic excitation is more nuanced and results from counteracting shifts in the repulsive (exchange) and attractive (electrostatic, induction and dispersion) forces. In particular, we show that the formation of additional binding N-H···π contacts in the relaxed S1 geometry is possible due to reduced Pauli repulsion in the excited state. The SAPT(CAS) interaction energies have been validated against the coupled cluster (CC) results and experimentally determined shifts of the S1 ← S0 anisole band. While for the hydrogen-bonded anisole-water dimer SAPT(CAS) and CC shifts are in excellent agreement, for ammonia SAPT(CAS) is only qualitatively correct.

Photothermal measurement of material properties for translucent thermal barrier coatings

In this study, a photothermal nondestructive method was proposed to measure the material parameters of semi-transparent or translucent thermal barrier coatings (TBCs). We derived a theoretical model for the photothermal signal from a two-layer semi-infinite material system with a translucent first layer after a pulse laser excitation. Its solution was verified by numerical solution. A data regression algorithm based on a least-squares fitting was used for the determination of the material parameters in the translucent first layer material. To verify this new method, an experimental system was set up with a pulse laser for thermal excitation and an infrared camera for image acquisition of the thermal emission transient from several translucent EBPVD TBC samples. The predicted coating thickness is consistent with the measured value by an optical microscope. The predicted thermal conductivity and optical attenuation coefficients in the absorption and emission band are found to be in good agreement with reference values.

Dual S-Scheme g-C3N4/Ag3PO4/g-C3N5 photocatalysts for removal of tetracycline pollutants through enhanced molecular oxygen activation

A dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction was prepared by decomposition methods, and it displayed enhanced performance to degrade tetracycline hydrochloride with the ideal stability under different water substrates and ions. Comparing with three single components, as g-C3N4, g-C3N5, and Ag3PO4, the dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction displayed 4.4-, 3.4-, and 2.5-times enhancements in the tetracycline hydrochloride removal. Based on the dynamics analyses for charge carriers and band structure calculations, two channels of molecular oxygen activation (MOA) between Ag3PO4 and g-C3N4 (and g-C3N5) were confirmed. More importantly, according to this double consumption process of excited electrons, dual S-scheme g-C3N4/Ag3PO4/g-C3N5 could suppress the charge recombination, which was the key point to boosting photocatalytic activity. Moreover, the determination of intermediates also supported the vital role of MOA during these photocatalytic reactions. this report of two reactive sites in MOA that generate reactive oxygen species in a “V” type band structure. The electronic dynamic in the reaction was also testified by several detections, indicating the enhanced charge separation and migration from internal field effect and electron trapping from dual S-scheme mechanism. This work provides a new research direction for the design and mechanism analysis of dual S-scheme photocatalysts

Vibronic Splitting of the Electronic Origin in Two Conformers of the 3-Tolunitrile Dimer.

3-tolunitrile (3-TN) can form three different dimers, which differ in the relative orientation of the methyl groups. We determined the geometry changes of two of these conformers of 3-TN upon electronic excitation via a Franck-Condon fit of the vibronic intensities in the fluorescence emission spectra. Both aromatic rings expand upon electronic excitation, showing a delocalized one-photon excitation of the cluster. The conformer with the smaller center-of-mass distance shows an unusual order of the split components of the electronic origin. We attribute this changed order to the stronger charge transfer contributions to the splitting and a partial breakdown of the point dipole approximation, made in the Frenkel type interaction.

Rank-Reduced Equation-of-Motion Coupled Cluster Triples: an Accurate and Affordable Way of Calculating Electronic Excitation Energies.

In the present work, we report an implementation of the rank-reduced equation-of-motion coupled cluster method with approximate triple excitations (RR-EOM-CC3). The proposed variant relies on tensor decomposition techniques in order to alleviate the high cost of computing and manipulating the triply excited amplitudes. In the RR-EOM-CC3 method, both ground-state and excited-state triple-excitation amplitudes are compressed according to the Tucker-3 format. This enables factorization of the working equations such that the formal scaling of the method is reduced to N6, where N is the system size. An additional advantage of our method is the fact that the accuracy can be strictly controlled by proper choice of two parameters defining sizes of triple-excitation subspaces in the Tucker decomposition for the ground and excited states. Optimal strategies of selecting these parameters are discussed. The developed method has been tested in a series of calculations of electronic excitation energies and compared to its canonical EOM-CC3 counterpart. Errors several times smaller than the inherent error of the canonical EOM-CC3 method (in comparison to FCI) are straightforward to achieve. This conclusion holds both for valence states dominated by single excitations and for states with pronounced doubly excited character. Taking advantage of the decreased scaling, we demonstrate substantial computational costs reductions (in comparison with the canonical EOM-CC3) in the case of two large molecules - l-proline and heptazine. This illustrates the usefulness of the RR-EOM-CC3 method for accurate determination of excitation energies of large molecules.

Controllable photoexfoliation of monolayer graphene quantum dots using temporally and spatially shaped femtosecond laser

Graphene quantum dots (GQDs) have displayed significant momentum in numerous fields due to their unique electronic properties. However, how to obtain uniformly monolayer quantum dots and explain the synthesis mechanism are still a key technical problem. Here, a rapid and controllable photoexfoliation rate of monolayer graphene quantum dots of up to 80 % was achieved by using temporally and spatially shaped femtosecond laser to ablate bulk highly oriented pyrolytic graphite targets in liquid. Theoretical calculations suggested that the temporally shaped laser can minimize the spatial range of electron excitation, maximize the Coulomb repulsion between the outer layers and Coulomb explosion within the topmost layer through multi-level electron excitation. The above multilevel photoexfoliations lead to the formation of monolayer GQDs. These findings demonstrate a perfect theoretical explanation of controllable and rapid preparation of monolayer quantum dots, accelerating its industrialization in energy storage devices.

The significant role of Z-scheme band alignment at the heterojunction for the enhanced photocatalytic H2 production in TiO2/BiNbO4/rGO nanocomposite

An efficient ternary TiO2/BiNbO4/rGO nanocomposite was prepared by a simple wet impregnation process. PXRD confirmed the tetragonal and orthorhombic crystalline natures of titanium dioxide (TiO2) and bismuth niobate (BiNbO4) respectively. The loading of BiNbO4 and reduced graphene oxide (rGO) shifted the light absorption of TiO2 to a longer wavelength from 400 to 430 nm. The suitable conduction band position of BiNbO4 facilitated a favourable band alignment to suppress the electron/hole (e−/h+) recombination in TiO2 via the Z scheme mechanism at the heterojunction. The excited electrons at the CB of TiO2 were easily transported via the fast electron accepting and conducting rGO matrix for the surface redox reactions with the improved charge transfer efficiency, which was confirmed by EIS and PL studies respectively. BiNbO4 and rGO synergistically improved the specific surface area and solar light absorption. EPR analysis confirmed the presence of increased oxygen vacancies at the heterojunction. Hence, the ternary TiO2/BiNbO4/rGO nanocomposite demonstrated an enhanced hydrogen evolution (8910 μ mol h−1 gcat−1) than bare TiO2 (4820 μ mol h−1 gcat−1), bare BiNbO4 (950 μ mol h−1 gcat−1) and TiO2/BiNbO4 (6730 μ mol h−1 gcat−1) under direct solar light. The optimum of 1 wt % BiNbO4 and rGO loaded TiO2 nanocomposite produced twice the H2 production than the bare TiO2. This also further confirms that rGO played a major role during the photocatalytic process by highlighting the potential of metal oxides combined with carbon material as an efficient photocatalyst which prominently enhances the H2 evolution.

Light-Induced Complete Reversal of Ferroelectric Polarization in Sliding Ferroelectrics.

Previous experiments have provided evidence of sliding ferroelectricity and photoexcited interlayer shear displacement in two-dimensional materials, respectively. Herein, we find that a complete reversal of vertical ferroelectric polarization can be achieved within an astonishing 0.5ps in h-BN bilayer by laser illumination. Comprehensive analysis suggests that ferroelectric polarization switching originates from laser-induced interlayer sliding triggered by selective excitation of multiple phonons. The interlayer electron excitation from the p_{z} orbitals of the upper layer N atoms to the p_{z} orbitals of the lower layer B atoms produces desirable and directional interlayer forces activating the in-plane optical TO-1 and LO-1 phonon modes. The atomic motions driven by the coupling of TO-1 and LO-1 modes are coherent with ferroelectric soft mode, thus modulating the dynamical potential energy surface and resulting in ultrafast ferroelectric polarization reversal. Our work provides a novel microscopic insight into ultrafast polarization switching in sliding ferroelectrics.

Ozone production in nanosecond pulsed dielectric barrier discharge in synthetic air: the Effect of Pulse Width

This work investigates the effect of pulse width on the characteristics of electrical discharge, optical emission spectra and ozone production in a water electrode DBD using a modulable nanosecond pulsed power supply. Results show that the increase of pulse width tpw slightly increases the spectral intensity and the rotational temperature Trot, with a typical Trot of 299 ± 5 K at an applied peak voltage Vp of 18.6 kV and a tpw of 400 ns. The electronic excitation temperature Texc increases linearly with Vp and gradually with tpw, while the electron density ne shows a non-linear relationship with tpw. Results also show that an increase in tpw slightly increases the energy density. At low energy densities (SIE < 50 J/L), increasing tpw can improve ozone generation efficiency, reaching a maximum of 99.64 ± 0.87 g/kWh at 33.60 ± 1.53 J/L at a tpw of 900 ns. This investigation provides substantial insight into the nanosecond pulsed ozone production.

Thermal effects on sound velocity peak and conformality in isospin QCD

We study thermal effects on equations of state (EOS) in isospin QCD, utilizing a quark-meson model coupled to a Polyakov loop. The quark-meson model is analyzed at one-loop that is the minimal order to include quark substructure constraints on pions which condense at finite isospin density. In the previous study we showed that the quark-meson model at zero temperature produces the sound velocity peak and the negative trace anomaly in the domain between the chiral effective theory regime at low density and the perturbative QCD regime at high density, in reasonable agreement with lattice simulations. We now include thermal effects from quarks in the Polyakov loop background and examine EOS, especially the sound velocity and trace anomaly along isentropic trajectories. At large isospin density, there are three temperature windows; (i) the pion condensed region with almost vanishing Polyakov loops, (ii) the pion condensed region with finite Polyakov loops, and (iii) the quark gas without pion condensates. In the domain (i), the gap associated with the pion condensate strongly quenches thermal excitations. As the system approaches the domain (ii), thermal quarks, which behave as nonrelativistic particles, add energy density but little pressure, substantially reducing the sound velocity to the value less than the conformal value while increasing the trace anomaly toward the positive value. Approaching the domain (iii), thermal quarks become more relativistic as pion condensates melt, increasing sound velocity toward the conformal limit. Corrections from thermal pions are also briefly discussed. Published by the American Physical Society 2024

Real-Time Observation of Frustrated Ultrafast Recovery from Ionization in Nanostructured SiO_{2} Using Laser-Driven Accelerators.

Ionizing radiation interactions in matter can trigger a cascade of processes that underpin long-lived damage in the medium. To date, however, a lack of suitable methodologies has precluded our ability to understand the role that material nanostructure plays in this cascade. Here, we use transient photoabsorption to track the lifetime of free electrons (τ_{c}) in bulk and nanostructured SiO_{2} (aerogel) irradiated by picosecond-scale (10^{-12} s) bursts of x rays and protons from a laser-driven accelerator. Optical streaking reveals a sharp increase in τ_{c} from <1 ps to >50 ps over a narrow average density (ρ_{av}) range spanning the expected phonon-fracton crossover in aerogels. Numerical modeling suggests that this discontinuity can be understood by a quenching of rapid, phonon-assisted recovery in irradiated nanostructured SiO_{2}. This is shown to lead to an extended period of enhanced energy density in the excited electron population. Overall, these results open a direct route to tracking how low-level processes in complex systems can underpin macroscopically observed phenomena and, importantly, the conditions that permit them to emerge.