State Energy Research Articles

Endo-Encapsulated Multi-Resonance Dendrimers with Through-Space Interactions for Efficient Narrowband Blue-Emitting Solution-Processed OLEDs.

Different from conventional luminescent dendrimers with fluorophore tethered outside to dendron, here we first developed endo-encapsulated luminescent dendrimers with multi-resonance (MR) fluorophore embedded inside of carbazole dendrons by growing dendrons through 1,8-positions of central carbazole moiety to create a cavity for accommodating the fluorophore. This endo-encapsulated structure not only shields the fluorophore to fully resist aggregation-caused spectral broadening, but also induce through-space interactions between dendron and fluorophore via intramolecular π-stacking, giving lowered singlet state energy and reduced singlet-triplet energy splitting to accelerate reverse intersystem crossing (RISC) from triplet to singlet states. The resultant dendrimer containing 1,8-linked second-generation carbazole dendrons and boron, sulfur-doped polycyclic MR fluorophore exhibits narrowband blue emission at 471 nm with FWHM kept at 34 nm even in neat film, together with ~4 times enhancement of RISC rate constant compared to its exo-tethered counterpart. Solution-processed OLEDs based on the endo-encapsulated dendrimer reveal efficient narrowband blue emissions with maximum external quantum efficiency of 22.6 %, representing the best device efficiency for blue-emitting multi-resonance dendrimers so far.

The electronic properties of a single electron in the GaAs/Ga1−xAlxAs oblate spheroidal quantum dot under the finite confinement potential

Quantum Dots, due to their fully quantized electronic states, have contributed to considerable progress in modern science and technology. Here we calculate the wave functions and energy spectrum of an electron confined in an oblate spheroidal quantum dot under the finite barrier potential condition, allowing the tailoring of the various energy states for specific applications. By calculating the electron wave functions outside the dot, we found that an infinite barrier is not a valid approximation for analyzing the optical properties of the structure. The effect of various geometrical and electrical characteristics of the structure, including the eccentricity, effective volume, and the height of barrier potential, is investigated. Additionally, the findings are compared with those found with prolate spheroidal quantum dot. The findings are further validated by comparing them to the exact electron energy level in a spherical quantum under the infinite barrier approximation.

Triaxial deformation, shell structure, shell corrections and the connection to alpha-clustering in nuclei

Abstract We explore the connection between the appearance of quasi-stable structures in mean-field type calculations, which arise as a result of the evolution of the underlying shell structure as a function of deformation, and α-clustering in light even–even nuclei. The Nilsson–Strutinsky mean-field approach employs a macroscopic liquid-drop whose energy is modified by a shell correction term derived using the Strutinsky method. This method reflects the variations in the energies of the single-particle states with deformation. As such, there is no obvious connection to clustering. Here we use the changing level scheme of the deformed harmonic oscillator as a function of triaxial deformation to fully explore the variation in stability of α-cluster structures in light even–even nuclei. The energies of the harmonic oscillator levels are used to deduce the energy required to disrupt the α-cluster as a function of the triaxial deformation. We find that there is good agreement between variations in the shell correction energy in the mean-field method and the energy required to disrupt the α-cluster. This provides a necessary link between understanding of the appearance of quasi-stable α-cluster structures and quasi-stable shapes appearing in mean-field calculations.

Ground State Energy of Dense Gases of Strongly Interacting Fermions

AbstractWe study the ground state energy of a gas of N fermions confined to a unit box in d dimensions. The particles interact through a two-body potential with strength scaled in an N-dependent way as $$N^{-\alpha }v$$ N - α v , where $$\alpha \in \mathbb {R}$$ α ∈ R and v is a function of positive type satisfying a mild regularity assumption. Our focus is on the strongly interacting case $$\alpha <1-\frac{2}{d}$$ α < 1 - 2 d . We contrast our result with existing results in the weakly interacting case $$\alpha >1-\frac{2}{d}$$ α > 1 - 2 d and the transition happening at the mean-field scaling $$\alpha =1-\frac{2}{d}$$ α = 1 - 2 d . Our proof is an adaptation of the bosonization technique used to treat the mean-field case.

Molecular electronic structure calculation via a quantum computer

Quantum computers can be used to calculate the electronic structure and estimate the ground state energy of many-electron molecular systems. In the present study, we implement the Variational Quantum Eigensolver (VQE) algorithm, as a hybrid quantum–classical algorithm to calculate the ground state energy of the molecules such as H3+, OH−, HF and BH3 in which the number of qubits has an increasing trend. We use the parity transformation for fermion to qubit encoding and the Unitary Coupled Cluster for Single and Double excitations (UCCSD) to construct an ansatz. We compare our quantum simulation results with the computational chemistry approaches including Full Configuration Interaction (FCI), as benchmark energy and Unrestricted Hartree–Fock (UHF), as a common computational method. Our results show that there is a good agreement between molecular ground state energy obtained from VQE and FCI. Moreover, the accuracy of the ground state energies obtained from VQE in our work is higher than the previously reported values. This work aims to benchmark the VQE algorithm to calculate the electronic ground state energy for a new set of molecules that can be good candidates for molecular simulation on a real quantum computer.

Helicene Covalent Organic Frameworks for Robust Light Harvesting and Efficient Energy Transfers.

Helicenes represent a class of fascinating π compounds with fused yet folded backbones. Despite their broad structural diversity, harnessing helicenes to develop well-defined materials is still a formidable challenge. Here we report the synthesis of crystalline porous helicene materials by exploring helicenes to synthesize covalent 2D lattices and layered π frameworks. Topology-directed polymerization of [6]helicenes and porphyrin creates 2D covalent networks with alternate helicene-porphyrin alignment along the x and y directions at a 1.5-nm interval and develops [6]helicene frameworks through reversed anti-AA stack along the z direction to form segregated [6]helicene and porphyrin columnar π arrays. Notably, this π configuration enables the frameworks to be highly red luminescent with benchmark quantum yields. The [6]helicene frameworks trigger effieicnt intra-framework singlet-to-singlet state energy transfer from [6]helicene to porphyrin and facilitate intermolecular triplet-to-triplet state energy transfer from frameworks to molecular oxygen to produce reactive oxygen species, harvesting a wide range of photons from ultraviolet to near-infrared regions for light emitting and photo-to-chemical conversion. This study introduces a new family of extended frameworks, laying the groundwork for exploring well-defined helicene materials with unprecedented structures and functions.

Boosted imaginary time evolution of matrix product states

In this work, we consider the imaginary time evolution of matrix product states. We present a quantum-inspired classical method that, when combined with time evolving block decimation (TEBD), is able to potentially speed up the convergence to a ground state compared to TEBD alone. Our method, referred to as boosted imaginary time evolution, relies on the use of reflections to boost to lower energy states. Interleaving TEBD steps with boosts reduces the total number of TEBD steps and potentially the computational cost required to imaginary time evolve a matrix product state to a ground state. We give the mathematical details of the method followed by an algorithmic implementation and finally some results for a simple test case. Published by the American Physical Society 2024

Large-stroke snap-through instability in the axial direction of a bi-stable structure with high slenderness

Mechanical snap-through instability of bi-stable structures may find many practical applications such as state switching and energy transforming. Although there exist diverse bi-stable structures capable of snap-through instability, it is still difficult for a structure with high slenderness to undergo the axial snap-through instability with a large stroke. Here, an elastic structure with high slenderness is simply constructed by a finite number of identical, conventional bi-stable units with relatively low slenderness in series connection. For realizing the axial snap-through instability with a large stroke, common scissors mechanisms are further introduced as rigid constraints to guarantee the synchronous snap-through instability of these bi-stable units. The global feature of the large-stroke snap-through instability realized here is robust and even insusceptible to the local out-of-synchronization of individual units. The present design provides a simple and feasible way to achieve the large-stroke snap-through instability of slender structures, which is expected to be particularly useful for state switching and energy transforming in narrow spaces.

Nanoscale Ga/Al substituted yttrium iron garnet films by liquid phase epitaxy

Yttrium iron garnet (YIG) has minimum damping factor and low ferromagnetic resonance (FMR) linewidth, making it a preferred material for low loss microwave and spintronic devices. The saturation magnetization of YIG is 1750 Gauss, and for low-frequency devices, a lower saturation magnetization is more suitable. Ga3+ and Al3+ are with smaller radii and non-magnetic moment, so the substitution of Ga3+ and Al3+ can decrease saturation magnetization. Here, 4.8–193.7 nm ultra-thin Y3(GaAlFe)5O12 garnet (GaAl-YIG) monocrystalline films are prepared on gadolinium gallium garnet (GGG) substrates by using the liquid-phase epitaxy (LPE) method. As expected, these films exhibit a low saturation magnetization of almost less than 100 Gauss, while their FMR linewidth remains at levels close to that of YIG. The films show a (111) orientation and in a state of tension, and the diffraction intensity of the films get stronger as films thickness increases. The free energy and density of states are calculated for different Ga/Al substitution position by density functional theory simulations. The elements show a different diffusion distance in the GaAl-YIG/GGG interface, and the variation of magnetization properties with interface width are analyzed. The surface roughness of the films is only a few angstroms. The damping factor of these ultra-thin films are on an order of 10−4 except the 4.8 nm film, which suggests that the minimum thickness of the garnet film with good performance by using the LPE method is about 10 nm. According to the analysis of structure and magnetization properties, it demonstrates that the LPE method has potential to provide nanoscale garnet films for low loss microwave and spintronic devices.

Molecular design of furanoacene-based singlet fission sensitizers combining diradical character and cross-substitution

Singlet fission (SF) suffers from the scarcity of available SF chromophores and sensitizers. Tetracene, pentacene and their derivatives, are two typical model systems for the study of SF photophysical phenomena. Herein, the analogues of polyacenes, furanoacenes and their derivatives, were evaluated as potential SF chromophores and sensitizers through a theoretical study. The primary photostability were evaluated by the frontier molecular orbital energy levels, diradical characters and SF relevant excited state energies according to the type-I and −II photodegradation mechanisms. The cross-substitutions by combining central substitutions with triple bonds and terminal substituents enhance photostability, tune the SF relevant excited states efficiently, and give more appropriate E(T1) to be SF sensitizers. This work helps to give better understanding of the electronic structures and SF capability of furanoacenes.

Existence of ground state sign-changing solutions for a class of quasilinear scalar field equations originating from nonlinear optics

This paper is mainly concerned with the existence of ground state sign-changing solutions for a class of second order quasilinear elliptic equations in bounded domains, which derived from nonlinear optics models. Combining a non-Nehari manifold method due to Tang and Cheng [J. Differ. Equations 261, 2384–2402 (2016)] and a quantitative deformation lemma with Miranda theorem, we obtain that the problem has at least one ground state solution and one ground state sign-changing solution with two precise nodal domains and we present the concrete lower bounds of ground state solution and ground state energy. We also obtain that any weak solution of the problem has C1,σ-regularity for some σ ∈ (0, 1). With the help of Maximum Principle, we reach the conclusion that the energy of the ground state sign-changing solutions is strictly larger than twice that of the ground state solutions.

Quantum Computation of Hydride Ion using Variational Quantum Algorithm

AbstractBecause of remarkable reactivity and strong electron‐electron correlation effects, the precise prediction of ground state energy and chemical reactivity of hydride ion is an essential objective in quantum chemistry. Leveraging variational quantum algorithms offers a promising avenue for studying molecular properties using current noisy intermediate‐scale quantum devices. This work utilises the variational approach to anticipate the ground state, reactivity, and single‐electron detachment energy of the three‐body hydride ion. We investigated both Hardware‐Efficient Ansatz (HEA) and Chemistry‐inspired ansatz based on a Unitary Coupled Cluster (UCC) on both noiseless and noisy IBM simulators. Modern error‐mitigating techniques, such as Zero‐Noise Extrapolation (ZNE) with unitary folding and measurement error mitigation, have been implemented to significantly reduce errors in noisy environments. This study contributes to our understanding of the quantum computational nuances of the hydride ion and addresses the question of whether quantum computers can retain the correlation energies for these correlated ions.

On the transition between two-phase and single-phase interface dynamics in ammonia sprays

This study explores the application of the density gradient theory to assess the validity of the two-phase spray atomization theory in multi-component ammonia sprays under conditions relevant to practical applications. The research focuses on analyzing the liquid–vapor interface structure at thermodynamic equilibrium. The most recent Helmholtz energy equation of state was employed to compute density profiles for ammonia and the surrounding nitrogen gas. The study investigates species distribution at equilibrium by examining minimal Helmholtz free energy states and evaluates critical parameters, such as interface thickness. The Knudsen number was also calculated as a temperature function to characterize the spray regime. The findings indicate that when the reduced temperature exceeds 0.95, a diffuse interface forms in ammonia-nitrogen systems, supporting using phase-field models for simulating ammonia injection in practical scenarios.

Mechanism and chemoselectivity of nitrile hydrosilylation catalyzed by [E-Rh] (E=Al, Ga, In) heterobimetallic catalysts: A theoretical perspective

Transition metals catalyzed hydrosilylation reaction is of significant values in organic synthesis. Herein the detailed mechanisms of the phenylacetonitrile hydrosilylation catalyzed by bimetallic [E-Rh] (E=Al, Ga, In) catalysts, as well as the RhCl(PPh3)3 monometallic catalyst, were investigated by DFT calculations. The electronic structure analysis indicates that the different atomic contributions of the Rh atom in E-Rh bond result in the polarity variations of the metal-metal bonds and different catalytic activities. The whole catalyzed cycle involves five processes: the formation of rhodium hydride complex, activation of H2SiMe2, insertion of phenylacetonitrile, reductive elimination, and isomerization. The reaction activities of [E-Rh] (E=Al, Ga, In) decrease successively, which is in agreement with the atomic contributions of Rh in three catalysts. DI analysis provides the evidence that the catalytic activity is controlled by the distortion energy of rate-determining state. QTAIM analysis shows the transformation of the Cl atom between two metal atoms, providing a clear description for structural changes in catalytic cycle.

Donor-Acceptor MOF Enabling Efficient Electrochemiluminescence Based on TSCT-TADF.

Electrochemiluminescence (ECL) is an extensively studied luminescence technique recognized for its efficacy in investigating surface energy states. Effective utilization of ECL to explore and probe the charge transfer mechanisms facilitated by novel luminescent materials is crucial. In this study, we demonstrate thermally activated delayed fluorescence (TADF) based on spatial charge transfer through the precisely controlled synthesis of luminescent materials, which is achieved by incorporating phenyl-carbazole derivatives as donor guests within acceptor-hosted metal-organic frameworks (D-A MOFs). These hybrid structures exhibit superior ECL intensities compared with their monomeric counterparts. Mechanistic investigation by DFT calculation reveals that the physically separated yet spatially closed D-A configuration induces efficient intermolecular through-spatial charge transfer (TSCT), leading to efficient ECL through tuning of the dihedral angle of the guest molecules to enhance π-π interactions. This study introduces a strategy for precise modulation of spatial charge transfer at the molecular level in the programmable synthesis of ECL luminophores.

Simultaneous path weak-measurements in neutron interferometry

The statistical properties of the detection events constituting the interference fringes at the output of an interferometer are well-known. Nevertheless, there is still no unified view of what is happening to a quantum system inside an interferometer. Strong measurements of path operators destroy the interference effect. In weak measurements, an observable is weakly coupled to a pointer system and the resulting weak values quantify the observable by minimally disturbing the system. Previous which-way experiments with weak measurements could extract either the real or imaginary part of a single weak value with each ensemble. Here, we present the simultaneous full complex quantification of two path weak values with a single ensemble in a Mach–Zehnder neutron interferometer. Magnetic fields, oscillating with different frequencies, change the energy state in each interferometer path. The time-dependent phase between the energy states distinctly marks each path. The resulting beating intensity modulation at the interferometer output gives both path weak values. For the present experiment, the weak values’ absolute value and phase directly describe the observed amplitude and phase of the intensity modulation.

Influences of hydrogen-bond promoting hydroxyl group on photophysical and catalytic properties of lanthanide pyridine dicarboxylate frameworks

To study the influences of hydrogen bonding interactions on photophysical properties and catalytic activities with insignificant interference from structural disparity, two new isostructural [LnIII2(OH-pda)(ox)2(H2O)4]∙4H2O coordination polymers (LnIII = EuIII (I) and NdIII (IIa), OH–H2pda = 4-hydroxypyridine-2,6-dicarboxylic acid, H2ox = oxalic acid) were synthesized and characterized. They are also isostructural to [NdIII2(pda)(ox)2(H2O)4]∙4H2O (IIb), H2pda = pyridine-2,6-dicarboxylic acid) containing pda2− instead of OH-pda2-. The identical framework structure of IIa and IIb with additional hydrogen bonding interactions in IIa due to –OH group of OH-pda2- has been presented. Based on IIa and IIb, the effects of the –OH group on photophysical properties and catalytic activities were then investigated without structural bias. With reference to the UV–vis absorption and phosphorescent emission spectroscopy, the singlet (S1) and triplet (T1) state energies of OH–H2pda (41,600 and 19,200 cm−1), H2pda (48,200 and 23,300 cm−1), OH-pda2- (IIa, 41,400 and 22,500 cm−1) and pda2− (IIb, 47,100 and 23,300 cm−1) were determined from which the influences of the –OH group have been revealed. Important roles of the –OH group as electron-donating group as well as hydrogen bond promoter have been proposed. Catalytic activities of IIa and IIb were comparatively examined using the solvent-free CO2 cycloaddition reaction at atmospheric pressure with epichlorohydrin in the presence of tetrabutylammonium bromide. The inferior performance of IIa (maximum yield of 62(±2)%) to IIb (maximum yield of 68(±2)%) was unexpectedly disclosed and the drawback of the substantial involvement of the catalytic sites in hydrogen bonding interactions has been demonstrated. Their reusability was additionally explored.

Artificial-intelligence-driven shot reduction in quantum measurement

Variational Quantum Eigensolver (VQE) provides a powerful solution for approximating molecular ground state energies by combining quantum circuits and classical computers. However, estimating probabilistic outcomes on quantum hardware requires repeated measurements (shots), incurring significant costs as accuracy increases. Optimizing shot allocation is thus critical for improving the efficiency of VQE. Current strategies rely heavily on hand-crafted heuristics requiring extensive expert knowledge. This paper proposes a reinforcement learning (RL)-based approach that automatically learns shot assignment policies to minimize total measurement shots while achieving convergence to the minimum of the energy expectation in VQE. The RL agent assigns measurement shots across VQE optimization iterations based on the progress of the optimization. This approach reduces VQE's dependence on static heuristics and human expertise. When the RL-enabled VQE is applied to a small molecule, a shot reduction policy is learned. The policy demonstrates transferability across systems and compatibility with other wavefunction Ansätze. In addition to these specific findings, this work highlights the potential of RL for automatically discovering efficient and scalable quantum optimization strategies.

A computational study and analysis of Variational Quantum Eigensolver over multiple parameters for molecules and ions

AbstractMaterial discovery is a phenomenon practiced since the evolution of the world. The discovery of materials has led to significant development in varied fields such as Science, Engineering and Technology. Computationally simulating molecules has been an area of interest in the industry as well as academia. However, simulating large molecules can be computationally expensive in terms of computing power and complexity. Quantum computing is a recent development that can improve the efficiency in predicting properties of atoms and molecules which will be useful for material design. The Variational Quantum Eigensolver (VQE) is one such quantum algorithm used to calculate the ground state energy of molecules or ions. In this study, we have done a comparative analysis of the parameters that constitute the VQE algorithm. This includes components such as basis, qubit mapping, ansatz, and optimizers used. We have also developed a database consisting of 79 single atoms and their variations of oxidation states and 33 molecules with the data of their Hamiltonian and ground state energy and dipole moment.

Absence of Additional Stretching-Induced Electron Scattering in Highly Conductive Cross-linked Nanocomposites with Negligible Tunneling Barrier Height and Width.

The intrinsic resistance of stretchable materials is dependent on strain, following Ohm's law. Here the invariable resistance of highly conductive cross-linked nanocomposites over 53% strain is reported, where additional electron scattering is absent with stretching. The in situ generated uniformly dispersed small silver nanosatellite particles (diameter=3.6nm) realize a short tunneling barrier width of 4.1nm in cross-linked silicone rubber matrix. Furthermore, the barrier height can be precisely controlled by the gap state energy level modulation in silicone rubber using cross-linkers. The negligible barrier height (0.01eV) and short barrier width, achieved by the silver nanosatellite particles in cross-linked silicone rubber, dramatically increase the electrical conductivity (51710Scm-1) by more than 4 orders of magnitude. The high conductance is also maintained over 53% strain. The quantum tunneling behavior is observed when the barrier height is increased, following the Simmons approximation theory. The transport becomes diffusive, following Ohm's law, when the barrier width is increased beyond 10.3nm. This study provides a novel strain-invariant resistance mechanism in highly conductive cross-linked nanocomposites.