Electronic Excitation Research Articles

Electronic excitations in the bulk of fractional quantum Hall states

Electronic excitations in the bulk of fractional quantum Hall states

Optimizing non-fullerene acceptor molecules constituting fluorene core for enhanced performance in organic solar cells: a theoretical methodology.

Looking for novel outstanding performance materials suitable for organic solar cells, we constructed a range of non-fullerene acceptors (NFAs) evolved from the recently synthesized acceptor molecule identified as DICTIF, structured around fluorene core where 2-(2,3-dihydro-3-oxo-1H-inden-1-ylidene) propanedinitrile presented the terminals end-groups. Employing density functional theory (DFT) and time dependent-DFT (TD-DFT) simulations, we have simulated the impact of altering the end groups of DICTIF molecule by five assorted acceptors molecules, for the purpose of exploring their opto-electronic properties and their performance in organic solar cell (OSC) applications. We proved that the designed non-fullerene acceptors provide enhanced efficiency compared to the synthesized molecule, such as planar geometries and narrower energy gap ranging from 1.51 to 1.95 eV. A red shift in absorption was observed for all tailored molecules (λmax = 583.5-711.4 nm) as compared to the reference molecule (λmax = 578 nm).Various decisive factors such as frontier molecular orbitals (FMOs), exciton binding energy (EB), absorption maximum (λmax), open circuit voltage (VOC), reorganization energies (RE), transition density matrix (TDM), reduced density gradient (RDG), and electron-hole overlap have also been computed for analyzing the performance of NFAs. Low reorganizational energy values facilitate charge mobility which improves the conductivity of all the designed molecules. This study showed that our novel tailored molecules might be suitable candidates for the fabrication of highly efficient photovoltaic materials. After testing various hybrid functionals, optimized geometries were assigned using DFT HSEH1PBE/6-31G(d) level of theory. Electronic excitations and absorption spectra were investigated using the TD-DFT MPW1PW91/6-31G(d) level of theory. We ascertained that HSEH1PBE/6-31G(d) level of theory yield the closest calculated highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the DICTIF to the corresponding experimental ones and that TD-MPW1PW91//6-31G(d) was the most suitable level of theory for exploring electronic excitations and finding the maximum of absorption (λmax).

Wide spectral range optical characterization of niobium pentoxide ([formula omitted]) films by universal dispersion model

In this work, the optical properties of niobium pentoxide (Nb2O5) films were extensively studied across a wide spectral range using heterogeneous data-processing methods, combining ellipsometric and spectrophotometric measurements for five samples with thicknesses between 20 and 250 nm. This study primarily determined the optical constants of Nb2O5 from the far infrared to the vacuum ultraviolet, presenting these constants as dispersion parameters using the universal dispersion model to describe valence electron excitations in ultraviolet region as well as phonon vibrations in infrared region. These comprehensive and reliable data across such a broad spectral range are unprecedented. Secondly, presented optical characterization proofs that Nb2O5 films can be grown without defects such as surface roughness, porosity, or inhomogeneity. This fact, together with its high refractive index, makes Nb2O5 a promising material for optical applications.

N-Aromatic Complexation in Tetraphenyl Porphyrin Iron (III)-Pyridine: Evidence of Spin-Flip via Gas-Phase Electronic Spectroscopy.

There is growing interest in the electronic properties of metalloporphyrins especially in relation to their interactions with other molecular species in their local environment. Here, UV-VIS laser photodissociation spectroscopy in vacuo has been applied to an iron-centred metalloporphyrin (FeTPP+) and its N-aromatic adduct with pyridine (py) to determine the electronic effect of complexation. Both the metalloporphyrin (FeTPP+) and pyridine adduct (FeTPP+⋅py) absorb strongly across the spectral region studied (652-302 nm: 1.91-4.10 eV). Notably, a large blue shift was observed for the dominant Soret band (41 nm) upon complexation (0.47±0.02 eV), indicative of strong pyridine binding. Significant differences in the profiles (i. e. number and position of bands) of the electronic spectra are evident comparing FeTPP+ and FeTPP+⋅py. Time-dependent density functional theory calculations were used to assign the spectra, revealing that the FeIII spin-state flips from S=3/2 to S=5/2 upon complexation with pyridine. For FeTPP+, all bright spectral transitions are found to be π-π* in character, with electron density variously distributed across the porphyrin and/or its phenyl substituents. Similar electronic excitations are observed for FeTPP+⋅py, with an additional bright transition which involves charge transfer from the porphyrin to the pyridine moiety.

Measurement of coherent vibrational dynamics with X-ray Transient Absorption Spectroscopy simultaneously at the Carbon K- and Chlorine L2,3- edges

X-ray Transient Absorption Spectroscopy (XTAS) is a powerful probe for ultrafast molecular dynamics. The evolution of XTAS signal is controlled by the shapes of potential energy surfaces of the associated core-excited states, which are difficult to directly measure. Here, we study the vibrational dynamics of Raman activated CCl4 with XTAS targeting the C 1s and Cl 2p electrons. The totally symmetric stretching mode leads to concerted elongation or contraction in bond lengths, which in turn induce an experimentally measurable red or blue shift in the X-ray absorption energies associated with inner-shell electron excitations to the valence antibonding levels. The ratios between slopes of different core-excited potential energy surfaces (CEPESs) thereby extracted agree very well with Restricted Open-Shell Kohn-Sham calculations. The other, asymmetric, modes do not measurably contribute to the XTAS signal. The results highlight the ability of XTAS to reveal coherent nuclear dynamics involving < 0.01 Å atomic displacements and also provide direct measurement of forces on CEPESs.

Calculation of Some Low-Lying Electronic Excitations of Barium Monofluoride Using the Equation of Motion (EOM)-CC3 Method with an Effective Core Potential Approach.

Barium monofluoride (BaF) is a polar molecule of interest in measurements of the electron electric dipole moment. For this purpose, efforts are underway to investigate this molecule embedded within cryogenic matrices, e.g., in solid Ne. For a theoretical understanding of the electronic structure of such an embedded molecule, the need arises for efficient methods which are accurate but also able to handle a number of atoms which surround the molecule. The calculation for gas-phase BaF can be reduced to involve only outer electrons by representing the inner core of Ba with a pseudopotential, while carrying out a non-relativistic calculation with an appropriate basis set. Thus, the method is effectively at a scalar-relativistic level. In this work, we demonstrate to which extent this can be achieved using coupled-cluster methods to deal with electron correlation. As a test case, the SrF(X2Σ+→B2Σ+) transition is investigated, and excellent accuracy is obtained with the EOM-CC3 method. For the BaF(X2Σ+→A'2Δ, X2Σ+→A2Π, X2Σ+→B2Σ+) transitions, various coupled-cluster approaches are compared with very good agreement for EOM-CC3 with experimentally derived spectroscopic parameters, at the level of tens of cm-1. An exception is the excitation to the A'2Δ state, for which the energy is overestimated by 230cm-1. The poor convergence behavior for this particular state is demonstrated by providing results from calculations with basis sets of n = 3, 4, 5)-zeta quality. The calculated excitation energy for the B2Σ+ state agrees better with a deperturbation analysis than with the effective spectroscopic value, with a difference of 120cm-1.

Time Resolved Quantum Tomography in Molecular Spectroscopy by the Maximal Entropy Approach.

Attosecond science offers unprecedented precision in probing the initial moments of chemical reactions, revealing the dynamics of molecular electrons that shape reaction pathways. A fundamental question emerges: what role, if any, do quantum coherences between molecular electron states play in photochemical reactions? Answering this question necessitates quantum tomography─the determination of the electronic density matrix from experimental data, where the off-diagonal elements represent these coherences. The Maximal Entropy (MaxEnt) based Quantum State Tomography (QST) approach offers unique advantages in studying molecular dynamics, particularly with partial tomographic data. Here, we explore the application of MaxEnt-based QST on photoexcited ammonia, necessitating the operator form of observables specific to the performed measurements. We present two methodologies for constructing these operators: one leveraging Molecular Angular Distribution Moments (MADMs) which accurately capture the orientation-dependent vibronic dynamics of molecules and another utilizing Angular Momentum Coherence Operators to construct measurement operators for the full rovibronic density matrix in the symmetric top basis. A key revelation of our study is the direct link between Lagrange multipliers in the MaxEnt formalism and the unique set of MADMs. Additionally, we visualize the electron density within the molecular frame, demonstrating charge migration across the molecule. Furthermore, we achieve a groundbreaking milestone by constructing, for the first time, the entanglement entropy of the electronic subsystem─a metric that was previously inaccessible. The entropy vividly reveals and quantifies the effects of coupling between the excited electron and nuclear degrees of freedom. Consequently, our findings open new avenues for research in ultrafast molecular spectroscopy within the broader domain of quantum information science, offering profound implications for the study of molecular systems under excitation using quantum tomographic schemes.

Development and characterization of atmospheric pressure gliding Arc plasma jet

In this work, we present the development and comprehensive characterization of an atmospheric pressure gliding arc plasma jet (GAPJ) operating in ambient air to generate non-thermal plasma. Through systematic investigation, the relationship between jet length and airflow rate indicates a positive correlation. Electrical and optical techniques are utilized to characterize the discharge, revealing an impact of applied voltage and gas flow rate on discharge parameters. Calculations are made for parameters such as electron density ((0.62−3.44)×1019) m −3, average power dissipation (9.85−40.50) W, and root mean square values of current and voltage. The impacts of applied voltages and gas flow rate on these parameters are also examined. Electron excitation temperature is determined using the Boltzmann plot method, yielding values within the range of (1.36−1.44) eV. Rotational and vibrational temperatures of discharge are analyzed, revealing values of (1373−2065) K and (2700−2405) K, respectively, under different operational conditions. The generated non-thermal plasma is confined to form a plasma plume although it consists of two diverging electrodes and offers promising applications for specified areas of sterilization and decontamination in the medical, pharmaceutical, and food processing industries.

Simulation of depth-dose curves and water equivalent ratios of energetic proton beams in cortical bone.

We have determined the depth-dose curve, penetration range, and water equivalent ratio for proton beams of clinical energies in cortical bone by means of a detailed and accurate simulation that combines molecular dynamics and Monte Carlo techniques. The fundamental input quantities (stopping power and energy loss straggling) for the simulation were obtained from a reliable electronic excitation spectrum of the condensed-phase target, which takes into account the organic and mineral phases that form it. Our simulations with these inputs, which are in excellent agreement with the scarce data available for a cortical bone target, deviate from simulations performed using other stopping quantities, such as those provided by the International Commission on Radiation Units and Measurements in its widely used Report No. 49 [M. J. Berger et al., Stopping powers and ranges for protons and alpha particles, International Commission on Radiation Units and Measurements, Bethesda, Maryland, 1993]. The results of this paper emphasize the importance of an accurate determination of the stopping quantities of cortical bone to advance towards the millimetric precision for the proton penetration ranges and deposited dose needed in radiotherapy.

Internal Conversion Cascade in a Carbon Nanobelt: A Multiconfigurational Quantum Dynamical Study.

Carbon nanobelts feature intriguing photophysical properties, due to their high symmetry and structural rigidity. Here, we consider a (6,6) armchair carbon nanobelt, i.e., the very first carbon nanobelt to be synthesized [Povie et al., Science 2017, 356, 172] and characterize the internal conversion dynamics using multiconfigurational quantum dynamics via the multi-layer multiconfiguration time-dependent Hartree (ML-MCTDH) method. A symmetry-adapted linear vibronic coupling Hamiltonian for 26 electronic states and 210 vibrational modes is employed. Electronic excitations are found to decay through a dense manifold of excited states, which interact via multiple conical intersections, while inducing minimal geometry change. It is shown that a rapid coherent decay, exhibiting a nonvanishing quantum flux on a time scale of less than 50 fs, transitions toward a slower, decoherent decay at longer times. As previously suggested in the literature, electronic relaxation is hindered by phonon bottlenecks such that a stepwise internal conversion cascade is observed. The computed vibronic absorption spectrum is shown to be in good agreement with the experimental spectrum.

Dynamical Correlations and Order in Magic-Angle Twisted Bilayer Graphene

The interplay of dynamical correlations and electronic ordering is pivotal in shaping phase diagrams of correlated quantum materials. In magic-angle twisted bilayer graphene, transport, thermodynamic, and spectroscopic experiments pinpoint a competition between distinct low-energy states with and without electronic order, as well as between localized and delocalized charge carriers. In this study, we utilize dynamical mean-field theory on the topological heavy fermion model of twisted bilayer graphene to investigate the emergence of electronic correlations and long-range order in the absence of strain. We contrast moment formation, Kondo screening, and ordering on a temperature basis and explain the nature of emergent correlated states based on three central phenomena: (i) the formation of local spin and valley isospin moments around 100 K, (ii) the ordering of the local isospin moments around 10 K preempting Kondo screening, and (iii) a cascadic redistribution of charge between localized and delocalized electronic states upon doping. At integer fillings, we find that low-energy spectral weight is depleted in the symmetric phase, while we find insulating states with gaps enhanced by exchange coupling in the zero-strain ordered phases. Doping away from integer filling results in distinct metallic states: a “bad metal” above the ordering temperature, where scattering off the disordered local moments suppresses electronic coherence, and a “good metal” in the ordered states with coherence of quasiparticles facilitated by isospin order. This finding reveals coherence from order as the microscopic mechanism behind the Pomeranchuk effect observed experimentally by Rozen [] and by Saito []. Upon doping, there is a periodic charge reshuffling between localized and delocalized electronic orbitals leading to cascades of doping-induced Lifshitz transitions, local spectral weight redistributions, and periodic variations of the electronic compressibility ranging from nearly incompressible to negative. Our findings highlight the essential role of charge transfer, hybridization, and ordering in shaping the electronic excitations and thermodynamic properties in twisted bilayer graphene and provide a unified understanding of the most puzzling aspects of scanning tunneling spectroscopy, transport, and compressibility experiments. Published by the American Physical Society 2024

Parametrization of Fluid Models for Electrical Breakdown of Nitrogen at Atmospheric Pressure

In the transient phase of an atmospheric pressure discharge, the avalanche turns into a streamer discharge with time. Hydrodynamic fluid models are frequently used to describe the formation and propagation of streamers, where charge particle transport is dominated by the creation of space charge. The required electron transport data and rate coefficients for the fluid model are parameterized using the local mean energy approximation (LMEA) and the local field approximation (LFA). In atmospheric pressure applications, the excited species produced in the electrical discharge determine the subsequent conversion chemistry. We performed the fluid model simulation of streamers in nitrogen gas at atmospheric pressure using three different parametrizations for transport and electron excitation rate data. We present the spatial and temporal development of several macroscopic properties such as electron density and energy, and the electric field during the transient phase. The species production efficiency, which is important to understand the efficacy of any application of non-thermal plasmas, is also obtained for the three different parametrizations. Our results suggest that at atmospheric pressure, all three schemes predicted essentially the same macroscopic properties. Therefore, a lower-order method such as LFA, which does not require the solution of the energy conservation equation, should be adequate to determine streamer macroscopic properties to inform most plasma-assisted applications of nitrogen-containing gases at atmospheric pressure.

Synthesis, characterization and effective UV photo-sensing properties of Ga3+ doped NiO nanoparticles

In this work, resistive type photodetectors were fabricated using Gd3+ ions doped NiO nanoparticles to improve the detection of ultraviolet (UV) light. The occurrence of the simple cubic phase in NiO systems has been shown by X-ray diffraction patterns. The crystalline size of the NiO nanoparticles doped with different concentrations of Gd3+ at levels of pure, 1 %, 2 %, and 3 % were 6 nm, 8 nm, 9 nm, and 12 nm, respectively. The presence of dopants in the material was established by the Raman spectrum analysis. Transmission electron microscopy (TEM) pictures were used to validate the morphological properties of Gd3+ doped NiO nanoparticles nanoparticles at different degrees of dopant concentration (0 %, 1 %, 2 % and 3 %). The introduction and concentration of dopants alter the shape of NiO material. Based on the findings of UV–visible absorption spectroscopic studies, it can be concluded that the addition of Gd3+ ions to the system improved the absorption characteristics. The measured bandgap values for various degrees of Gd3+ doping, namely 0 %, 1 %, 2 %, and 3 %, are 3.51 eV, 3.45 eV, 3.36 eV, and 3.23 eV, respectively. According to the measured photoluminescence spectrum, Gd3+ ions may efficiently trap and maintain excited electrons within an energy level between the ground and excited states. This process greatly extends the lifespan of excitons from immediate recombination. The use of Gd3+-doped NiO sensors in UV photodetection resulted in a significant increase in conductivity and photocurrent. The photodetector fabricated using a 3 % concentration of Gd3+ doped NiO, has a responsivity of 24 × 10−2 AW−1, a detectivity of 14 × 109 Jones, and an external quantum efficiency (EQE) of 62 %.

Bloch-Wave Phase Matching of High Harmonic Generation in Solids.

There has been a longstanding doubt that the conversion efficiency of high harmonics in solids is much lower than expected at such a high level of electron density. To address this issue, we revisit the dynamical process of high harmonic generation (HHG) in solids in terms of wavelet interference. We find that the constructive interference among the wavelets has intrinsic consistency with the phase matching of coupled waves in nonlinear optics, which we call Bloch-wave phase matching. Our analysis indicates that most of the wavelets are out of phase and coherently canceled out during the solid HHG process, leading to only a small fraction of excited electrons effectively contributing to HHG. Consequently, the conversion from the excited electron to HHG is fairly low. Moreover, a Bloch-wave phase-matching scheme is proposed and a nearly 3 orders of magnitude enhancement of solid HHG can be achieved by engineering the crystal structures. Our Letter addresses a longstanding doubt and provides a novel idea and theoretical guidance for realizing efficient all-solid-state tabletop ultraviolet light sources.

Computational Modeling of the Conformation-Dependent Atmospheric Reactivity of Criegee Intermediates.

The impacts of Criegee intermediates (CIs) on atmospheric chemistry depend significantly on the CI conformation. In this Perspective, I highlight examples of how electronic structure and statistical rate theory calculations, in conjunction with experiment, have revealed conformation-dependent details of both CI ground-state reactivity and electronic excitation. Calculations using single-reference electronic structure methods and conventional transition state theory have predicted that CIs with syn-alkyl or syn-vinyl substituents isomerize rapidly to vinyl hydroperoxides (VHPs) or dioxoles, both of which can decompose rapidly under atmospheric conditions. Ongoing computational research on hydroxyl radical (OH) roaming initiated by VHP dissociation requires the application of multireference electronic structure methods and variational transition state theory. CIs that lack both syn-alkyl and syn-vinyl substituents undergo either bimolecular reaction or π* ← π electronic excitation in the atmosphere. Accurate predictions of CI ultraviolet-visible spectra require multireference calculations with large active spaces and at least a second-order perturbative treatment of dynamic electron correlation. The extent to which electronic spectra can be diagnostic of the presence of specific CI conformers varies significantly with CI chemical identity.

Discrimination of vibrational modes in Ni2MnGa thin films

Vibrational properties in magnetic shape memory alloys are intrinsically connected to the topologies formed due to temperature-dependent breakdown of symmetry. In this sense, herein, we apply Raman spectroscopy in the study of Ni2MnGa films prepared by sputtering on glass and gallium arsenide substrates. Different laser wavelengths probe the Raman active vibrational modes. The non-equilibrium heating mechanisms of the electronic lattice induced by excitation laser power within the thermal penetration depth are used to explain the formation of higher order vibrational modes resulting from phonon-assisted intra-band electronic excitations. The discrimination of the Raman active modes is performed based on calculations carried out within the framework of the density functional theory considering the coexistence of austenite and martensite phases as a function of temperature in films with different crystalline textures and residual stresses. More importantly, this work presents a simple way to discriminate the vibrational modes of the austenite and martensite phases in Ni2MnGa thin films that can be easily applied in the nanodevice development process.

Effects of applied pressure on structural, electronic, and optical properties of magnesium incorporated wurtzite beryllium oxide at different magnesium compositions

The effects of applied pressure on the structural, electronic, and optical properties of magnesium-incorporated wurtzite beryllium oxide (w-BeO) at different magnesium compositions are calculated. Each compound at different applied pressures confirms stability in the wurtzite phase. At different applied pressures, the equilibrium lattice constants (a0, c0) increase, but the bulk modulus (B0) and the c0/a0 ratio decrease with increasing magnesium composition. With increasing pressure, the lattice constants of each specimen decrease nonlinearly. Each compound possesses a wide direct band gap (Г-Г) at different applied pressures. The calculated band gap decreases with increasing magnesium composition at different applied pressures. With an increase in applied pressure, the band gap of each compound increases. Each wurtzite specimen is optically anisotropic and exhibits birefringence. Electronic excitations from O-2p to Be-2s, 3p and Mg-3s, 3p are responsible for the various optical features of the considered alloys. At different applied pressures, static optical constants ε1(0), n(0), and R(0) increase, but critical points in the ε2(ω), k(ω, σ(ω), and α(ω) spectra decrease with increasing magnesium composition. For each specimen, components of static optical constants reduce, while components of critical point energies increase with an increase in applied pressure.

Compact modeling of highly excited linear aggregates using generalized quantum particles

Calculation of nonlinear spectra of chromophore aggregates using response function theory when the number of contributing chromophores is large, and the level of excitation is high is extremely complicated. The main limitation is due to the exponential growth of computational time due to the aggregate size and number of excitations when considering an arbitrary excitation intensity. Non-perturbative calculation of spectra in this case becomes advantageous. We revisit our proposed model with exciton - exciton annihilation terms and apply it to large aggregates. We generalize the equations for both paulions and bosons with a parameter that allows smooth transition from one description to another. Intermediate statistics may also be valuable as molecular electronic excitations do not strictly obey either boson or paulion statistics. Specific approximations allow efficient calculation of pump-probe spectra for a large J aggregate.

Weyl fermion excitations in the ideal Weyl semimetal CuTlSe2

An ideal Weyl semimetal is characterized by a dispersion in which only Weyl cones intersect the Fermi level, with low-energy behavior being governed by Weyl fermions. Although ideal Weyl semimetals have long been anticipated, only a few are realized in nonmagnetic materials. In this study, we confirm the presence of Weyl-fermion excitations in the ideal Weyl semimetal CuTlSe2 via a combination of magnetoresistance, Hall-effect, magnetic-susceptibility, nuclear magnetic resonance (NMR), and muon-spin relaxation (µSR) experiments. Magnetoresistance measurements reveal a negative longitudinal magnetoresistance (LMR), which scales as B2, while Hall-effect results indicate a predominant contribution from Weyl fermions with a hole-type charge. Magnetic susceptibility and µSR measurements indicate the lack of any intrinsic spontaneous magnetic moments down to base temperature. Finally, the NMR results can be modeled by a two-component effective Hamiltonian, which reproduces well the temperature-dependent Cu63 NMR (T1T)−1 factor, shown to scale as T2 below 100 K and as T1 above 100 K. Overall, we find that the extremely low concentration (1017cm−3) of carriers in CuTlSe2 originates from an ideal nonmagnetic Weyl semimetallic state, persisting up to a thermal excitation energy of 9 meV (100 K), above which trivial electronic bands close to EF take over. Our findings highlight CuTlSe2 as a new member of the intriguing class of Weyl semimetals. Published by the American Physical Society 2024

Monte Carlo calculations of cryogenic photodetector readout of scintillating GaAs for dark matter detection

The recent discovery that GaAs(Si,B) is a bright cryogenic scintillator with no apparent afterglow offers new opportunities for detecting rare, low-energy, electronic excitations from interacting dark matter. This paper presents Monte Carlo calculations of the scintillation photon detection efficiencies of optical cavities using three current cryogenic photodetector technologies. In order of photon detection efficiency these are: (1) Ge/TES: germanium absorbers that convert interacting photons to athermal phonons that are readout by transition edge sensors, (2) KID: kinetic induction detectors that respond to the breaking of cooper pairs by a change in resonance frequency, and (3) SNSPD: superconducting nanowire single photon detectors, where a photon briefly transitions a thin wire from superconducting to normal. The detection efficiencies depend strongly on the n-type GaAs absolute absorption coefficient KA, which is a part of the narrow beam absorption that has never been directly measured. However, the high cryogenic scintillation luminosity of GaAs(Si,B) sets an upper limit on KA of 0.03/cm. Using that value and properties published for Ge/TES, KID, and SNSPD photodetectors, this work calculates that those photodetectors attached to opposing faces of a 1 cm3 cubic GaAs(Si,B) crystal in an optical cavity with gold mirrors would have scintillation photon detection efficiencies of 35%, 25%, and 8%, respectively. Larger values would be expected for lower values of KA.