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The core levels of TIBa(sub 2)CaCu(sub 2)O(sub 7-delta) epitaxial films have been measured with x-ray photoelectron spectroscopy (XPS). The valence electronic structure has been determined using the full-potential linear muffin tin orbital band structure method and measured with XPS.
The catalytic activity of transition metal sulfide (TMS) clusters in small molecule activation, redox transformations, and charge transfer has inspired the design of novel TMS-based materials for energy-related catalysis and chemical applications. Polyoxometalates (POMs), known for their structural diversity, can in principle be transformed into TMS clusters; however, fully sulfided analogs are rarely isolated, likely due to the strong tendency of uncapped TMS clusters to agglomerate. Here, we report the geometric and electronic structure of a capping ligand-free fully sulfided analog of heptamolybdate Anderson POM [Mo VI 7 O 24 ] 6− , synthesized through the sulfidation of a nanoconfined POM secured within a porous Zr-metal organic framework (NU-1000). A combined computational and experimental analysis indicates that the sulfided counterpart of the Anderson POM is geometrically and electronically more sophisticated than the parent POM. Comparison of experimental pair distribution function (PDF) data with computational simulations confirms that, unlike the oxygen-only [Mo VI 7 O 24 ] 6− cluster, the [Mo IV 7 (μ 3 -S) 6 (μ 2 -SH) 6 (S 2 ) 6 ] 2− polythiometalate (PTM) exhibits diverse sulfur anions (S 2− , HS − , S 2 2− ). DFT calculations indicate that H 2 S acts as a reducing agent, and together with terminal disulfide (S 2 2− ) ligands in the PTM structure, facilitates the complete reduction of all seven Mo VI centers in the parent POM to Mo IV . These findings are supported by X-ray photoelectron spectroscopy (XPS), which confirms exclusive Mo IV , and elemental analysis, which shows quantitative sulfur incorporation. Difference envelope density (DED) mapping further reveals that the PTM clusters are spatially confined within the MOF pores, preventing agglomeration and preserving molecular integrity.
Here, we introduce a novel open-source software package QForte, a comprehensive development tool for new quantum simulation algorithms. QForte incorporates functionality for handling molecular Hamiltonians, fermionic encoding, ansatz construction, time evolution, and state-vector emulation, requiring only a classical electronic structure package as a dependency. QForte also contains black-box implementations of a wide variety of quantum algorithms, including variational and projective quantum eigensolvers, adaptive eigensolvers, quantum imaginary time evolution, and quantum Krylov methods. We highlight two features of QForte: (i) how the Python class structure of QForte enables the facile implementation of new algorithms, and (ii) how existing algorithms can be executed in just a few lines of code.
There has been an upsurge in the discovery of topological quantum materials, where various topological insulators and semimetals have been theoretically predicted and experimentally observed. However, very few of them contain silicon, the most widely used element in the electronics industry. Recently, ternary compound CaA l 2 S i 2 has been predicted to be a topological Dirac semimetal, hosting Lorentz-symmetry-violating quasiparticles with a strongly tilted conical band dispersion. In this work, by using high-resolution angle-resolved photoemission spectroscopy, we investigated the comprehensive electronic structure of CaA l 2 S i 2 . A pair of topological Dirac crossings is observed along the k z direction, in good agreement with the ab initio calculations, confirming the topological Dirac semimetal nature of the compound. Our study expands the topological material family on Si-containing compounds, which have great application potential in realizing low-cost, nontoxic electronic devices with topological quantum states.
Six zinc(II) porphyrins bearing 0–4 meso-phenyl substituents have been examined spectroscopically and theoretically. Comparisons with previously examined free base analogues afford a deep understanding of the electronic and photophysical effects of systematic addition of phenyl groups in porphyrins containing a central zinc(II) ion versus two hydrogen atoms. Trends in the wavelengths and relative intensities of the absorption bands are generally consistent with predictions from time-dependent density functional theory calculations and simulations from Gouterman’s four-orbital model. These trends derive from a preferential effect of the meso-phenyl groups to raise the energy of the highest occupied molecular orbital. The calculations reveal additional insights, such as a progressive increase in oscillator strength in the violet-red (B-Q) absorption manifold with increasing number of phenyls. Progressive addition of 0–4 phenyl substituents to the zinc porphyrins in O 2 -free toluene engenders a reduction in the measured lifetime of the lowest singlet excited state (2.5–2.1 ns), an increase in the S 1 → S o fluorescence yield (0.022–0.030), a decrease in the yield of S 1 → T 1 intersystem crossing (0.93–0.88), and an increase in the yield of S 1 → S o internal conversion (0.048–0.090). The derived rate constants for S 1 decay reveal significant differences in the photophysical properties of the zinc chelates versus free base forms. Here, the unexpected finding of a larger rate constant for internal conversion for zinc chelates versus free bases is particularly exemplary. Collectively, the findings afford fundamental insights into the photophysical properties and electronic structure of meso-phenylporphyrins, which are widely used as benchmarks for tetrapyrrole-based architectures in solar energy and life sciences research.
Dissipative engineering is a powerful tool for quantum state preparation, and has drawn significant attention in quantum algorithms and quantum many-body physics in recent years. In this work, we introduce a novel approach using the Lindblad dynamics to efficiently prepare the ground state for general ab initio electronic structure problems on quantum computers, without variational parameters. These problems often involve Hamiltonians that lack geometric locality or sparsity structures, which we address by proposing two generic types of jump operators for the Lindblad dynamics. Type-I jump operators break the particle number symmetry and should be simulated in the Fock space. Type-II jump operators preserves the particle number symmetry and can be simulated more efficiently in the full configuration interaction space. For both types of jump operators, we prove that in a simplified Hartree-Fock framework, the spectral gap of our Lindbladian is lower bounded by a universal constant. For physical observables such as energy and reduced density matrices, the convergence rate of our Lindblad dynamics with Type-I jump operators remains universal, while the convergence rate with Type-II jump operators only depends on coarse grained information such as the number of orbitals and the number of electrons. To validate our approach, we employ a Monte Carlo trajectory-based algorithm for simulating the Lindblad dynamics for full ab initio Hamiltonians, demonstrating its effectiveness on molecular systems amenable to exact wavefunction treatment.
We report copper-based delafossite oxides are excellent candidates for the p-type transparent conducting oxide (TCO), which is essential in realizing transparent semiconductor applications. Using angle-resolved photoemission spectroscopy (ARPES), we report the low-energy electronic structure of CuAlO 2 . We found that the band structure near the valence band top is characterized by hole bands with their maxima along the Brillouin zone boundary. Furthermore, the effective masses along the Γ–M and Γ–K directions were found to be (0.6 ± 0.1) m0 and (0.9 ± 0.1) m 0 , respectively, which impose an important benchmark against the existing band calculations.
We report the development of a novel diagnostic tool, named wave function overlap tool (WFOT), designed to evaluate the overlap between wave functions computed at single-reference [i.e., time-dependent density functional theory or configuration interaction singles (CIS)] and multireference (i.e., CASSCF/CASPT2) electronic structure levels of theory. It relies on truncating the single- and multireference WFs to CIS-like expansions spanning the same configurational space and maximizing the molecular orbital overlap by means of a unitary transformation. To demonstrate the functionality of the tool, we calculate the transient spectrum of acetylacetone by evaluating excited state absorption signals with multireference quality on top of single-reference on-the-fly dynamics simulations. Semiautomatic spectra generation is facilitated by interfacing the tool with the COBRAMM package, which also allows one to use WFOT with several quantum chemistry codes such as Gaussian, NWChem, and OpenMolcas. Finally, other exciting possibilities for the utilization of the code beyond the simulation of transient absorption spectroscopy are eventually discussed.
block2 is an open source framework to implement and perform density matrix renormalization group and matrix product state algorithms. Out-of-the-box it supports the eigenstate, time-dependent, response, and finite-temperature algorithms. In addition, it carries special optimizations for ab initio electronic structure Hamiltonians and implements many quantum chemistry extensions to the density matrix renormalization group, such as dynamical correlation theories. The code is designed with an emphasis on flexibility, extensibility, and efficiency and to support integration with external numerical packages. Here, we explain the design principles and currently supported features and present numerical examples in a range of applications.
High-entropy alloys (HEAs) have attracted great attention due to their many unique properties and potential applications. The nature of interatomic interactions in this unique class of complex multicomponent alloys is not fully developed or understood. We report a theoretical modeling technique to enable in-depth analysis of their electronic structures and interatomic bonding, and predict HEA properties based on the use of the quantum mechanical metrics, the total bond order density (TBOD) and the partial bond order density (PBOD). Application to 13 biocompatible multicomponent HEAs yields many new and insightful results, including the inadequacy of using the valence electron count, quantification of large lattice distortion, validation of mechanical properties with experiment data, modeling porosity to reduce Young’s modulus. This work outlines a road map for the rational design of HEAs for biomedical applications.
A collaborative effort between experiment and theory towards elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAu n – (n=3-7) were taken at third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193nm) photon energies, where the experimental adiabatic electron affinities (AEA) and vertical detachment energies (VDE) values were measured. Complementary first principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu 6 where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAu n clusters (n = 3 - 7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UF n species, but significant deviations are seen starting with UAu 5 where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu 6 system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are to be nearly isoenergetic. With UAu 7 , only ring-like structures are calculated. Altogether, the calculated electron detachment energies are in good agreement with the experimental values
The continuous demand for efficient, nontoxic, and thermally stable materials for room-temperature energy conversion motivates the exploration of novel thermoelectric systems beyond the traditional magnetic Heusler alloys. While full and half-Heusler compounds, especially Co-, Ni-, and Mn-based systems, have demonstrated promising thermoelectric properties, their typically high operating temperatures and magnetic complexities limit their applicability in ambient thermal management. In this context, we investigate whether Sc-based inverse Heusler alloys can offer a viable nonmagnetic alternative with competitive thermoelectric performance. In this work, we perform a systematic first-principles study of the inverse Heusler compounds Sc 2 RuZ (Z = Si, Ge, Sn), focusing on their structural, electronic, mechanical, and thermodynamic-thermoelectric properties. Density Functional Theory (DFT) was employed to compute optimized lattice structures and band dispersion, while dynamical stability was assessed via phonon calculations. Thermoelectric transport coefficients, including Seebeck coefficient, electrical conductivity, and thermal conductivity, were estimated using the semiclassical Boltzmann transport theory within the constant relaxation time approximation. Our results show that all Sc 2 RuZ compounds are thermodynamically stable semiconductors with indirect band gaps of 0.12–0.16 eV and exhibit high elastic moduli, especially Sc 2 RuSn, which demonstrates superior stiffness and incompressibility. Importantly, all compounds display promising room-temperature thermoelectric characteristics, including high Seebeck coefficients and power factors. These findings reveal that Sc 2 RuZ alloys represent a rare class of stable, nonmagnetic inverse Heusler semiconductors with intrinsic thermoelectric potential at room temperature, unlike many existing Heusler systems optimized for spintronics or high-temperature operation. This work expands the known design space for Heusler-based thermoelectrics and offers a theoretical basis for experimental realization of efficient, low-temperature, nonmagnetic thermoelectric materials.
Iron–sulfur clusters are crucial for biological electron transport and catalysis. Obtaining accurate geometries, energetics, manifolds of their excited electronic states, and reduction energies is important to understand their role in these processes. Here, using a [2Fe–2S] model complex with Fe II and Fe III oxidation states, which leads to different charges, i.e., [Fe 2 S 2 (SMe) 4 ] 2–,3–,4– , we benchmarked a variety of computational methodologies ranging from density functional theory (DFT) to post-Hartree–Fock methods, including complete active space self-consistent field (CASSCF), multireference configuration interaction, the second-order N-electron valence state perturbation theory (NEVPT2), and the linearized integrand approximation of adiabatic connection (AC0) approaches. Additionally, we studied three experimentally well-characterized complexes, [Fe 2 S 2 (SCys) 4 ] 2– , [Fe 2 S 2 (S-o-tol) 4 ] 2– , and [Fe 2 S 2 (S-o-xyl) 4 ] 2– , via DFT methods. We conclude that the dynamic electron correlation is important for accurately predicting the geometry of these complexes. Broken symmetry (BS) DFT correctly predicts experimental geometries of low-spin multiplicity, while CASSCF does not. However, BS-DFT significantly overestimates the difference between the low- and high-spin electronic states for a given oxidation state. At the same time, CASSCF underestimates it but provides relative energies closer to the reference NEVPT2 results. Finally, AC0 provides energetics of NEVPT2 quality with the additional advantage of being able to use large CASSCF sizes. NEVPT2 gives the best estimates of the Fe III /Fe III → Fe II /Fe III (4.27 eV) and Fe II /F III → Fe II /F II (7.72 eV) reduction energies. The results provide insight into the electronic structure of these complexes and assist in the understanding of their physical properties.
We report the time-resolved femtosecond evolution of the K-shell X-ray emission spectra of iron during high intensity illumination of X-rays in a micron-sized focused hard X-ray free electron laser (XFEL) beam. Detailed pulse length dependent measurements revealed that rapid spectral energy shift and broadening started within the first 10 fs of the X-ray illumination at intensity levels between 10 17 and 10 18 W cm -2 . We attribute these spectral changes to the rapid evolution of high-density photoelectron mediated secondary collisional ionization processes upon the absorption of the incident XFEL radiation. These fast electronic processes, occurring at timescales well within the typical XFEL pulse durations (i.e., tens of fs), set the boundary conditions of the pulse intensity and sample parameters where the widely-accepted ‘probe-before-destroy’ measurement strategy can be adopted for electronic-structure related XFEL experiments.
SmAgSb 2 , a layered magnetic semimetal in the tetragonal 𝑅𝑇 Sb 2 family (𝑅 = Y, Sc, rare earth; 𝑇 = transition metal), is known to exhibit extremely large magnetoresistance (XMR) below its antiferromagnetic (AFM) transition temperature. Here, in this work, we present a comprehensive investigation combining magnetotransport measurements, density functional theory calculations accounting for electron correlation, and angle-resolved photoemission spectroscopy. Our results reveal a complex electronic structure characterized by a multiband Fermi surface and intricate magnetic ground states. We demonstrate that simple two-band models, previously employed in the literature, fail to consistently describe the observed transport phenomena. Notably, we report an XMR of approximately 25200% at 2 K under a 14 T magnetic field, significantly exceeding earlier reports for this material family and rivaling the performance of prominent nonmagnetic XMR systems. This pronounced enhancement below 𝑇 𝑁 suggests that the XMR originates from a combination of multiband electron-hole compensation and enhanced magnetic scattering in this correlated AFM semimetal.
This project report consists of the following three sections: A.) Investigation of Charge Transport Properties in Semiconducting Conjugated Polymer Blends Using Computational Chemistry and Experiments: This section provides unpublished but valuable research results that correlate the electronic structure of PCBM:PCDTBT organic photovoltaic systems with their current-voltage characteristics. The presentation is structured in the form of a scientific publication. B.) Scanning Probe Microscopy Methodology Development Efforts for Organic Photovoltaic Materials: This section summarizes various published works focusing on advancements in scanning probe microscopy methods. Each sub-section corresponds to a scientific publication for which the abstract and citation are provided. C.) Other Publications Supported by the Project: This section lists additional published works partially supported by the project, which are not included in the previous two sections.
Two thiophosphates, KInP 2 S 7 and KCrP 2 S 7 , were structurally characterized without investigating any optical properties. Herein in this work, KInP 2 S 7 and KCrP 2 S 7 were revisited to investigate their optical and magnetic properties, respectively. Pure polycrystalline samples and crystals of KInP 2 S 7 and KCrP 2 S 7 were grown by high temperature solid state reactions, where mm-sized crystals of KCrP 2 S 7 were collected. KCrP 2 S 7 is isostructural to KInP 2 S 7 , which features a layered structure. KInP 2 S 7 and KCrP 2 S 7 possess close relationship to the layered thiophosphate M 2 P 2 S 6 (M = Fe, Co, Zn, etc.). The bonding pictures of KInP 2 S 7 were studied using the electron localization function (ELF) coupled with crystal orbital Hamilton population (COHP) calculations. The intrinsically distorted [PS 4 ] tetrahedra and [InS 6 ] octahedra are made by strong covalent P-S interactions and ionic In-S interactions, respectively. Electronic structure analysis confirmed that the optical properties of KInP 2 S 7 are mainly contributed to by [PS 4 ] tetrahedra together with small amounts of the contributions coming from [InS 6 ] octahedra. Magnetic measurement on mm-sized crystals of KCrP 2 S 7 verified that there is an antiferromagnetic transition around 21 K, and the Cr atoms are trivalent. KInP 2 S 7 is predicated to be an indirect bandgap semiconductor of 2.38 eV, which is confirmed by the UV-Vis measurement of 2.4(1) eV. KInP 2 S 7 is not a type-I phase-matching material and exhibits moderate second harmonic generation (SHG) response (0.51 × AgGaS 2 , sample of particle size of 100 µm). The laser damage threshold (LDT) of KInP 2 S 7 is very high of 5.2 × AgGaS 2 . Bandgap engineering were undergone to enhance the SHG response of KInP 2 S 7 .
Abstract A member of the RMn 6 Sn 6 rare-earth family materials, TbMn 6 Sn 6 , recently showed experimental signatures of the realization of a quantum-limit Chern magnet. In this work, we use quantum Monte Carlo (QMC) and density functional theory with Hubbard U (DFT + U ) calculations to examine the electronic structure of TbMn 6 Sn 6 . To do so, we optimize accurate, correlation-consistent pseudopotentials for Tb and Sn using coupled-cluster and configuration–interaction (CI) methods. We find that DFT + U and single-reference QMC calculations suffer from the same overestimation of the magnetic moments as meta-GGA and hybrid density functional approximations. Our findings point to the need for improved orbitals/wavefunctions for this class of materials, such as natural orbitals from CI, or for the inclusion of multi-reference effects that capture the static correlations for an accurate prediction of magnetic properties. DFT + U with Mn magnetic moments adjusted to the experiment predict the Dirac crossing in bulk to be close to the Fermi level, within ~120 meV, in agreement with the experiments. Our non-stoichiometric slab calculations show that the Dirac crossing approaches even closer to the Fermi level, suggesting the possible realization of Chern magnetism in this limit.