Excitation Energy Research Articles

Excitation configuration analysis for divide-and-conquer excited-state calculation method using dynamical polarizability.

The authors previously developed a divide-and-conquer (DC)-based non-local excited-state calculation method for large systems using dynamical polarizability [Nakai and Yoshikawa, J. Chem. Phys. 146, 124123 (2017)]. This method evaluates the excitation energies and oscillator strengths using information on the dynamical polarizability poles. This article proposes a novel analysis of the previously developed method to obtain further configuration information on excited states, including excitation and de-excitation coefficients of each excitation configuration. Numerical applications to simple molecules, such as ethylene, hydrogen molecule, ammonia, and pyridazine, confirmed that the proposed analysis could accurately reproduce the excitation and de-excitation coefficients. The combination with the DC scheme enables both the local and non-local excited states of large systems with an excited nature to be treated.

Interaction between lateral jet and hypersonic rarefied flow

Reaction control systems (RCS) are commonly utilized in a variety of air vehicles, and they give rise to complex flow phenomena. For flows dominated by shock waves and expansion, such as lateral jets, a significant gradient is formed in the local region of the flow field, resulting in a high local Knudsen number, and the continuum hypothesis is no longer applicable, even if the freestream belongs to near-continuum flow. As a result, multi-scale simulation approaches should be used to capture the interactions between these multi-scale structures and appropriately determine aerodynamic forces. Our earlier work, which used the conserved discrete unified gas kinetic scheme (CDUGKS) for monatomic gas, studied the flow field features of lateral jets and aerodynamic forces on blunt bodies under various rarefied freestream conditions. In this research, the Rykov model is used to expand the CDUGKS suit for diatomic gas flow while taking into account the excitation of molecular rotational energy. The impact on the flow field and aerodynamic forces from four parameters, namely freestream Mach number, jet Mach number, jet pressure ratio, and nozzle position, is thoroughly investigated. The results show that even if the incoming Mach number is different, the flow field structure and aerodynamic properties don't change much when the jet momentum ratio stays the same. The solid wall stagnation point value and local peak also show some linear relationships. The jet pressure ratio mainly affects the expansion characteristics of the jet, such as the influence range on the solid wall. In addition, with an increase in the distance between the nozzle position and the torque reference point, higher control efficiency can be obtained. The study of these aspects will help us comprehend lateral jet flow and provide reference for the design of an air vehicle's RCS.

Investigation of the M1 transitions from the ground configuration of W23+

To extend the research on the atomic structure of tungsten ions with an open 4f-shell, we conducted an investigation into the M1 transitions originating from the ground configuration of W23+ using the SHHtscEBIT in the 420–600 nm range. Three different calculational methods, including the relativistic configuration interactions (RCI) and the relativistic many-body perturbation theory (RMBPT) implemented in FAC, as well as the multiconfiguration Dirac-Hartree-Fock (MCDHF) in GRASP2018, are performed to investigate the energy level structure of W23+. The excitation energies obtained through RCI and RMBPT are in good agreement, with an average difference of 0.62 %. When comparing RCI and MCDHF, this difference increases to 1.20 %. The observed 12 lines of W23+are identified using the detailed collisional-radiative model with the atomic data calculated by RCI. The average wavelength deviations from experimental results are 0.77 %, 1.38 %, and 2.02 % for RCI, RMBPT, and MCDHF, respectively.

Nonadiabatic molecular dynamics with subsystem density functional theory: application to crystalline pentacene

In this work, we report the development and assessment of the nonadiabatic molecular dynamics approach with the electronic structure calculations based on the linearly scaling subsystem density functional method. The approach is implemented in an open-source embedded Quantum Espresso/Libra software specially designed for nonadiabatic dynamics simulations in extended systems. As proof of the applicability of this method to large condensed-matter systems, we examine the dynamics of nonradiative relaxation of excess excitation energy in pentacene crystals with the simulation supercells containing more than 600 atoms. We find that increased structural disorder observed in larger supercell models induces larger nonadiabatic couplings of electronic states and accelerates the relaxation dynamics of excited states. We conduct a comparative analysis of several quantum-classical trajectory surface hopping schemes, including two new methods proposed in this work (revised decoherence-induced surface hopping and instantaneous decoherence at frustrated hops). Most of the tested schemes suggest fast energy relaxation occurring with the timescales in the 0.7–2.0 ps range, but they significantly overestimate the ground state recovery rates. Only the modified simplified decay of mixing approach yields a notably slower relaxation timescales of 8–14 ps, with a significantly inhibited ground state recovery.

Ultrafast terahertz Stark spectroscopy reveals the excited-state dipole moments of retinal in bacteriorhodopsin

The photoinduced all-trans to 13-cis isomerization of the retinal Schiff base represents the ultrafast first step in the reaction cycle of bacteriorhodopsin (BR). Extensive experimental and theoretical work has addressed excited-state dynamics and isomerization via a conical intersection with the ground state. In conflicting molecular pictures, the excited state potential energy surface has been modeled as a pure S[Formula: see text] state that intersects with the ground state, or in a 3-state picture involving the S[Formula: see text] and S[Formula: see text] states. Here, the photoexcited system passes two crossing regions to return to the ground state. The electric dipole moment of the Schiff base in the S[Formula: see text] and S[Formula: see text] state differs strongly and, thus, its measurement allows for assessing the character of the excited-state potential. We apply the method of ultrafast terahertz (THz) Stark spectroscopy to measure electric dipole changes of wild-type BR and a BR D85T mutant upon electronic excitation. A fully reversible transient broadening and spectral shift of electronic absorption is induced by a picosecond THz field of several megavolts/cm and mapped by a 120-fs optical probe pulse. For both BR variants, we derive a moderate electric dipole change of 5 [Formula: see text] 1 Debye, which is markedly smaller than predicted for a neat S[Formula: see text]-character of the excited state. In contrast, S[Formula: see text]-admixture and temporal averaging of excited-state dynamics over the probe pulse duration gives a dipole change in line with experiment. Our results support a picture of electronic and nuclear dynamics governed by the interaction of S[Formula: see text] and S[Formula: see text] states in a 3-state model.

Prediction of the 1st excitation energy of odd–odd nuclei with the Bayesian neural network approach

A Bayesian neural network (BNN) is developed to predict the 1st excitation energy of odd–odd nuclei. Aside from the proton number and neutron number, we introduce two empirical physical quantities into the input layer. δ=[−1N+−1Z]/2 is introduced to distinguish even–even, odd–odd and odd-A nuclei; and the so-called Casten factor P≡vpvnvp+vn is introduced to stand for collectivity. The BNN is trained with an experimental dataset of the 1st excitation energy for 434 odd–odd, 649 even–even and 1050 odd-A nuclei. After training, the BNN predicts the 1st excitation energy of odd–odd nuclei with a rms of 0.21 MeV. Examples of Dy, Gd, Eu and Cs isotopes are also shown. The BNN results show moderate predictive ability, in comparison with results from the projected Hartree–Fock method.

Independent isomeric yield ratios of fission products in the epi-cadmium neutron induced fission of 239Pu

Measurement of independent isomeric yield ratios (IR) of 128,130,132Sb, 131,133Te, 132.134,136I, 135Xe and 138Cs have been carried out for the first time in the epi-cadmium neutron induced fission of 239Pu by using an off-line gamma-ray spectrometric technique. The average neutron energy (<En>) of the epi-cadmium reactor neutron spectrum is 1.9 MeV. From the IR values, root mean square fragment angular momenta (JRMS) were deduced by using spin dependent statistical model analysis. Effect of nuclear structure on JRMS values was examined. The present data in the epi-cadmium neutron induced fission of 239Pu were compared with the similar data in the thermal neutron induced fission of 239Pu to examine the role of excitation energy on JRMS values.

Enhanced visible light photocatalytic activity of SDBS/C/Nd/TiO2 synthesized by using anionic surfactant SDBS as template agent

&lt;p&gt;The catalyst SDBS/C/Nd/TiO2 was synthesized by sol-gel method using TiO2 co-doped with C and Nd and anionic surfactant SDBS as template agent. The prepared photocatalysts were characterized by X-ray diffraction (XRD), scanning electron (SEM), X-ray photoelectron spectrometer (XPS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS) and so on. Experimental results show that the crystal structure of the catalytic material is anatase type. Since doped elements change the energy band structure and electronic structure of TiO2, photogenerated electrons and holes can transition through the intermediate energy level, resulting in a decrease in the required excitation energy, thereby increasing the distance of its absorption edge moving toward the long wave direction, and meanwhile improving the utilization rate of visible light. The bandgap energy of the catalyst SDBS/C/Nd/TiO2 was 2.78 eV. Compared to pure TiO2 (3.1 eV), the band gap is reduced by 0.32eV. The photocatalytic experiments show that the degradation rate of the catalyst SDBS/C/Nd/TiO2 for methyl orange solution can reach 67%, and the catalytic performance is much improved than that of pure TiO2.&lt;/p&gt;

Systematic Engineering of Near-Infrared Small Molecules Based on 4H-Cyclopenta[1,2-b:5,4-b']dithiophene Acceptors for Organic Solar Cells.

Nonfullerene acceptors (NFAs) have emerged as tremendous materials, efficiently advancing bulk-heterojunction organic solar cells (OSCs) technology. Unlike their fullerene counterparts, NFAs offer the unique advantage of finely tunable electronic energy levels and optical characteristics, which correspond to substantial enhancement in power conversion efficiency of OSCs. Herein, we have introduced a new series of near-infrared NFAs (AY1-AY8) to advance this technology further. Our research deeply investigates the structure-property relationship and thoroughly explores the optical, optoelectronics, photophysical, and photovoltaic characteristics of a synthetic reference molecule (R) and the modeled AY1-AY8 NFAs series. We performed advanced quantum chemical simulations using density functional theory (DFT) and time-dependent DFT methods. Additionally, we also estimated key geometric characteristics such as frontier molecular orbitals, hole-electron overlap, density of states, molecular electrostatic potential, molecular excitation and binding energies, transition density matrix, and reorganizational energy of electrons and holes and compared them with those of a synthetic reference molecule (R). Our findings show that all designed materials (AY1-AY8) exhibit red-shift absorption, improved electronic charge mobility, and low binding and excitation energies compared to R. Notably, these designed materials (AY1-AY8) display significantly narrower electronic energy gaps (E g 1.89-1.71 eV), indicating enhanced charge shifting from the highest occupied molecular orbital to lowest unoccupied molecular orbital and broadening of the absorption spectrum. Moreover, we also revealed a comprehensive study of the donor/acceptor complex of PTB7-Th/AY8 to understand charge shifting between donor and acceptor molecules. Therefore, we strongly recommend this designed (AY1-AY8) series to the experimentalists for the future development of highly efficient OSC devices.

A note on degeneracy of excited energy levels in massless Dirac fermions

We propose a mechanism to construct the eigenvalues and eigenfunctions of the massless Dirac-Weyl equation in the presences of magnetic flux Φ localized in a restricted region of the plane. Using this mechanism we analyze the degeneracy of the existed energy levels. We find that the zero and first energy level has the same N+1 degeneracy, where N is the integer part of Φ2π. In addition, and contrary to what is described in the literature regarding graphene, we show that higher energy levels are N+m degenerate, being m the level of energy. In other words, this implies an indefinite growth of degenerate states as the energy level grows.

Single-Electron Qubits Based on Quantum Ring States on Solid Neon Surface.

Single electrons trapped on solid-neon surfaces have recently emerged as a promising platform for charge qubits. Experimental results have revealed their exceptionally long coherence times, yet the actual quantum states of these trapped electrons, presumably on imperfectly flat neon surfaces, remain elusive. In this Letter, we examine the electron's interactions with neon surface topography, such as bumps and valleys. By evaluating the surface charges induced by the electron, we demonstrate its strong perpendicular binding to the neon surface. The Schrödinger equation for the electron's lateral motion on the curved 2D surface is then solved for extensive topographical variations. Our results reveal that surface bumps can naturally bind an electron, forming unique quantum ring states that align with experimental observations. We also show that the electron's excitation energy can be tuned using a modest magnetic field to facilitate qubit operation. This study offers a leap in our understanding of electron-on-solid-neon qubit properties and provides strategic insights on minimizing charge noise and scaling the system to propel forward quantum computing architectures.

Unveiling the Multifaceted Nature of 4‐(4‐Methylphenyl Thio)benzophenone: Electronic Structure and Excited States in Gas Phase and Solvents

AbstractBenzophenone and its derivatives are widely used as UV filters and UV‐ink photoinitiators. The photoinitiating properties of benzophenones depend on their degree of conjugation and delocalization within the molecule. By understanding how conjugation, delocalization, and different substituents affect these properties, benzophenone derivatives can be customized for specific applications. Using quantum mechanical calculations based on B3LYP/6‐311++G(d, p) density functional theory (DFT), chemical reactivity, stability, and photoinitiating capabilities of 4‐(4‐methylphenylthio)benzophenone are analyzed. This includes studying its physical and chemical properties in the gas phase, as well as its excited state electronic transitions, vibrational characteristics, and spectroscopic properties both in gas phase and in various solvents. The DFT‐computed infrared spectra match experimental results. The UV/Visible spectra shows absorption towards longer wavelengths due to extended delocalization of π‐electrons. In different solvents with varying polarity, the absorption spectra exhibit high‐intensity peaks, shift in excitation energy and wavelengths based on the polarity of the solvent. This knowledge allows for the development of novel initiators with customized light absorption, excited state lifetimes, and reaction selectivities, which can enhance processes like UV‐curing, photopolymerization, and other light‐driven reactions.

Fast Photocatalytic Hydrogen Peroxide Generation by Singlet Oxygen-Engaged Sequential Excitation Energy and Electron-Transfer Process

Fast Photocatalytic Hydrogen Peroxide Generation by Singlet Oxygen-Engaged Sequential Excitation Energy and Electron-Transfer Process

Reference Energies for Double Excitations: Improvement and Extension.

In the realm of photochemistry, the significance of double excitations (also known as doubly excited states), where two electrons are concurrently elevated to higher energy levels, lies in their involvement in key electronic transitions essential in light-induced chemical reactions as well as their challenging nature from the computational theoretical chemistry point of view. Based on state-of-the-art electronic structure methods (such as high-order coupled-cluster, selected configuration interaction, and multiconfigurational methods), we improve and expand our prior set of accurate reference excitation energies for electronic states exhibiting a substantial amount of double excitations [Loos et al. J. Chem. Theory Comput. 2019, 15, 1939]. This extended collection encompasses 47 electronic transitions across 26 molecular systems that we separate into two distinct subsets: (i) 28 "genuine" doubly excited states where the transitions almost exclusively involve doubly excited configurations and (ii) 19 "partial" doubly excited states which exhibit a more balanced character between singly and doubly excited configurations. For each subset, we assess the performance of high-order coupled-cluster (CC3, CCSDT, CC4, and CCSDTQ) and multiconfigurational methods (CASPT2, CASPT3, PC-NEVPT2, and SC-NEVPT2). Using as a probe the percentage of single excitations involved in a given transition (%T1) computed at the CC3 level, we also propose a simple correction that reduces the errors of CC3 by a factor of 3, for both sets of excitations. We hope that this more complete and diverse compilation of double excitations will help future developments of electronic excited-state methodologies.

Effects of donor substituents on the conformational heterogeneity, photophysical, mechanochromic and electroluminescent properties of the donor-substituted fluorine-containing triphenylpyrimidines

Three derivatives of fluorinated triphenylpyrimidine with the attached carbazole, phenothiazine, or acridan donor moieties are synthesized by Buchwald-Hartwig reactions. The impact of the donor units on emissive and other properties of the compounds is reported. The compounds exhibit excellent thermal stability, competitive photophysical phenomena such as room temperature phosphorescence (RTP) appearing when compounds are molecularly dispersed in the rigid polymer matrix and thermally activated delayed fluorescence (TADF). The compounds with carbazole and phenothiazine donor moieties show the manifestation of triplet–triplet annihilation in the electroluminescence when used as emitters in organic light-emitting diodes (OLEDs). The phenothiazine-containing compound exhibit dual photoluminescence with the blue-shifted peak corresponding to the quasi-axial conformer and a red-shifted peak to the quasi-equatorial conformer. This derivative shows reversible shifts of emission spectra exceeding 100 nm due to the stable (at least 4 cycles) mechanochromic luminescence under the application of external stimuli. After grinding the emission intensity maximum is observed at 555 nm, after fuming at. ca 448 nm and after melting at 555 nm. The photoluminescence shifts and ON/OFF delayed fluorescence of the phenothiazine-based emitter occur due to the alteration between the crystalline and amorphous states. Optimization of the device structure allows to control the charge balance resulting in external quantum efficiency of up to 5.7 % observed for the OLED based on the phenothiazine-based emitter. This compound also shows the biggest response to the presence of oxygen acting as the quencher of triplet excited energy. The film of the compound doped in rigid Zeonex shows an 8.4-fold increase in emission intensity after evacuation. The optical sensor fabricated using the derivative of fluorinated triphenylpyrimidine and phenothiazine is characterized by the Stern-Volmer constant 1.37 × 10-4 ppm−1.

Implementation of theoretical non-photochemical quenching (NPQ(T)) to investigate NPQ of chickpea under drought stress with High-throughput Phenotyping

Non-photochemical quenching (NPQ) is a protective mechanism for dissipating excess energy generated during photosynthesis in the form of heat. The accelerated relaxation of the NPQ in fluctuating light can lead to an increase in the yield and dry matter productivity of crops. Since the measurement of NPQ is time-consuming and requires specific light conditions, theoretical NPQ (NPQ(T)) was introduced for rapid estimation, which could be suitable for High-throughput Phenotyping. We investigated the potential of NPQ(T) to be used for testing plant genetic resources of chickpea under drought stress with non-invasive High-throughput Phenotyping complemented with yield traits. Besides a high correlation between the hundred-seed-weight and the Estimated Biovolume, significant differences were observed between the two types of chickpea desi and kabuli for Estimated Biovolume and NPQ(T). Desi was able to maintain the Estimated Biovolume significantly better under drought stress. One reason could be the effective dissipation of excess excitation energy in photosystem II, which can be efficiently measured as NPQ(T). Screening of plant genetic resources for photosynthetic performance could take pre-breeding to a higher level and can be implemented in a variety of studies, such as here with drought stress or under fluctuating light in a High-throughput Phenotyping manner using NPQ(T).

Transient Chiral Dynamics in the Fenna-Matthews-Olson Complex Revealed by Two-Dimensional Circular Dichroism Spectroscopy.

Chirality plays a pivotal role across scientific disciplines with profound implications spanning light-matter interactions, molecular recognition, and natural evolutionary processes. This study delves into the active influence of molecular chirality on exciton energy transfer within photosynthetic protein complexes, focusing on the Fenna-Matthews-Olson (FMO) complex. Employing two-dimensional circular dichroism (2DCD) spectroscopy, we investigate the transient chiral dynamics of excitons during energy transfer processes within the FMO complex. Our approach, incorporating pulse information into population dynamics based on the third-order response function, facilitates the calculation of 2DCD spectra and dynamics. This enables the extraction of chiral contributions to excitonic energy transfer and the examination of electronic wave functions. We demonstrate that 2DCD spectra offer excitation energies that are better resolved than those from conventional two-dimensional electronic spectroscopy. These findings deepen our understanding of exciton energy transfer mechanisms in natural photosynthesis, emphasizing the potential of 2DCD spectroscopy as a powerful tool for unraveling the chiral contribution to exciton dynamics.

Highly-Polarized Emission Provided by Giant Optical Orientation of Exciton Spins in Lead Halide Perovskite Crystals.

Quantum technologic and spintronic applications require reliable material platforms that enable significant and long-living spin polarization of excitations, the ability to manipulate it optically in external fields, and the possibility to implement quantum correlations between spins, i.e., entanglement. Here it is demonstrated that these conditions are met in bulk crystals of lead halide perovskites. A giant optical orientation of 85% of excitons, approaching the ultimate limit of unity, in FA0.9Cs0.1PbI2.8Br0.2 crystals is reported. The exciton spin orientation is maintained during the exciton lifetime of 55ps resulting in high circular polarization of the exciton emission. The optical orientation is robust to detuning of the excitation energy up to 0.3eV above the exciton resonance and remains larger than 20% up to detunings of 0.9eV. It evidences pure chiral selection rules and suppressed spin relaxation of electrons and holes, even with large kinetic energies. The exciton and electron-hole recombinations are distinguished by means of the spin dynamics detected via coherent spin quantum beats in magnetic field. Further, electron-hole spin correlations are demonstrated through linear polarization beats after circularly polarized excitation. These findings are supported by atomistic calculations. All-in-all, the results establish lead halide perovskite semiconductors as suitable platform for quantumtechnologies.

Nonlinear vibration energy harvesting via parametric excitation: Snap-through with time-varying potential wells

This study introduces a novel method to improve snap-through transitions in a parametrically excited cantilever-based energy harvester featuring repulsive magnetic coupling. The aim is to enhance the efficiency of a piezoelectric energy harvester while broadening its operational frequency range. The design incorporates an oscillating substructure that magnetically interacts with the beam, promoting easier transitions. Additionally, this setup capitalizes on the resonant energy of the substructure to optimize energy capture. This study addresses a previously unexplored limitation in the directly excited counterpart by optimizing the use of substructure’s resonant energy to significantly improve the energy harvesting device’s efficiency. We present a theoretical model based on the Hamilton principle, which is solved numerically. Comprehensive experimental studies are conducted to validate the theoretical results, showing a strong correlation between the experimental outcomes and theoretical predictions. The findings indicate that an oscillating substructure with a tailored natural frequency close to twice that of the parametrically excited piezoelectric beam can induce time-varying potential wells to facilitate snap-through transitions. Despite the damping coefficient of the piezoelectric beam being three times higher than that of its simple beam counterpart, periodic perturbations still effectively expand its instability region. This enlarged instability region, resulting from such perturbations, not only exhibits broadband characteristics but also facilitates efficient energy harvesting at lower excitation levels.

Simultaneously boosting visible and near-infrared luminescence of Ho in Cs2AgInCl6 double perovskites via Bi3+ sensitization

The emergence of near-infrared (NIR) luminescence from lanthanide (Ln3+) ions doped lead-free Cs2AgInCl6 double perovskites (DPs) has garnered significant attention due to its extensive range of potential applications. Unfortunately, they still suffer from weak NIR emission due to the inherent wide band gap of DPs resulting in inefficient energy transfer from the host to Ln3+. Herein, Bi3+ can act as the sensitizer to activate Ho3+ emission and reduce the excitation energy in Cs2AgInCl6: Ho. Under 400 nm excitation, Bi3+ co-doped Cs2AgInCl6: Ho shows 39 times and 21 times higher emission intensity than Cs2AgInCl6: Ho in Visible and NIR. As a result, a photoluminescence quantum yield of 18.63 % ranging from 800 to 1600 nm can be obtained. Finally, by coupling a Bi-doped sample with a commercial near-ultraviolet LED chip (395 nm), a compact Vis-NIR ultrawideband light source was prepared, which has promising applications in multifunctional illumination and night vision.