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Light-induced structural changes of the photosynthetic membrane protein reaction centre from Bl. viridis as determined by time-resolved wide angle X-ray scattering at the Linac Coherent Light Source X-ray free-electron laser. Magnitude of movement enhanced for clarity.
Two new bismuth(III) selenite/tellurite nitrates, [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}), have been synthesized by conventional facile hydrothermal method at middle temperature 200 °C and characterized by single-crystal X-ray diffraction, powder diffraction, UV–vis–NIR optical absorption spectrum, infrared spectrum and thermal analylsis. Both [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO3)](NO3) crystallize in the monoclinic centronsymmetric space group P2{sub 1}/c with a=9.9403(4) Å, b=9.6857(4) Å, c=10.6864(5) Å, β=93.1150(10)° for [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and a=8.1489(3) Å, b=9.0663(4) Å, c=7.4729(3) Å, β=114.899(2)° for Bi(TeO3)(NO3), respectively. The two compounds, whose structures are composed of three different asymmetric building units, exhibit two different types of structures. The structure of [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) features a three-dimensional (3D) bismuth(III) selenite cationic tunnel structure [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}] {sup 3}{sub ∞} with NO{sub 3}{sup −} anion group filling in the 1D tunnel along b axis. The structure of [Bi(TeO{sub 3})](NO{sub 3}) features 2D bismuth(III) tellurite [Bi(TeO{sub 3}){sub 2}]{sup 2}{sub ∞} layers separated by NO{sub 3}{sup −} anion groups. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory methods show that the two compounds are wide band-gap semiconductors. - Graphical abstract: Two novel bismuth{sup III} selenite/tellurite nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) with 3D tunnel structure and [Bi(TeO{sub 3})](NO{sub 3}) with 2D layer structure have been firstly synthesized and characterized. Display Omitted - Highlights: • Two novel bismuth{sup III} nitrates [(Bi{sub 3}O{sub 2})(SeO{sub 3}){sub 2}](NO{sub 3}) and [Bi(TeO{sub 3})](NO{sub 3}) were firstly synthesized. • The two compounds were wide band-gap semiconductors.
Accounting for disorder in anatase titanium nitride fluoride TiNF is done through atoms re-distributions based on geometry optimizations using ultra soft pseudo potentials within density functional theory DFT. The fully geometry relaxed structures are found to keep the body centering of anatase (I4{sub 1}/amd No. 141). The new structural setups are identified with space groups I-4m2 No. 119 and Imm2 No. 44 which obey the 'group to subgroup' relationships with respect to anatase. In the ground state Imm2 structure identified from energy differences, TiNF is found semi-conducting with similar density of states features to anatase TiO{sub 2} and a chemical bonding differentiated between covalent like Ti-N versus ionic like Ti-F. Inter-anion N-F bonding is also identified. - Graphical Abstract: The geometry optimized ground state anatase derived TiNF structure with arrangement of open faceted TiN3F3 distorted octahedra. The insert shows the arrangement of octahedra in anatase TiO{sub 2}. Highlights: Black-Right-Pointing-Pointer Original approach of TiNF structure for addressing the electronic band structure. Black-Right-Pointing-Pointer Based on anatase, two different ordering scheme models with geometry optimization. Black-Right-Pointing-Pointer New structures obeying the group{yields}subgroup relationships with Imm2 ground state from energy. Black-Right-Pointing-Pointer In the ground state TiNF is found semi-conducting with similar density of states to anatase TiO{sub 2}. Black-Right-Pointing-Pointer Chemical bonding differentiated between covalent like Ti-N and ionic Ti-F.
The structural, electronic, and magnetic properties of Ti{sub 2}RhSn{sub 1-x}Si{sub x}, Ti{sub 2}RhSn{sub 1-x}Ge{sub x}, and Ti{sub 2}RhGe{sub 1-x}Si{sub x} (x = 0, 0.25, 0.5, 0.75, and 1) quaternary Heusler alloys have been investigated using first-principles density functional theory within generalized gradient approximation (GGA) and local spin-density approximation with Hubbard-U corrections (LSDA+U). The calculations have been performed using the full-potential linearized augmented Plane wave plus local orbitals method. The crystal structures of Ti{sub 2}RhSn{sub 1-x}Si{sub x}, Ti{sub 2}RhSn{sub 1-x}Ge{sub x}, and Ti{sub 2}RhGe{sub 1-x}Si{sub x} were found to be cubic in (F-43m) symmetry for x = 0, 1 and cubic in (P-43m) symmetry for x = 0.25, 0.75, while tetragonal in (P-4m2) symmetry for x = 0.5. The results show that all Ti{sub 2}RhSn1-xSix, Ti{sub 2}RhGe{sub 0.75}Si{sub 0.25}, and Ti{sub 2}RhGe alloys are half-metallic ferrimagnetic. These new materials are good candidates for potential applications in spintronic.
Using methods of the density functional theory, the electronic band structure of a hexagonal modification of the layered GaTe semiconductor has been calculated. The structural parameters of a bulk crystal with the β-polytype symmetry have been determined taking into account van der Waals interactions and agree with experimental data for polycrystalline films within 2%. Estimates for the position of extrema of the upper valence band and the lower conduction band have been obtained with respect to the vacuum level for bulk β-GaTe and for ultrathin plates with the number of elementary layers ranging from 1 to 10, which corresponds to a thickness range of 0.5–8 nm. The calculations demonstrate that hexagonal GaTe is an indirect band gap semiconductor with a forbidden band width varying from 0.8 eV in the bulk material to 2.3 eV in the monolayer.
Relative stabilities of small Ga{sub n}As{sub m} clusters, as well as their structural electronic and vibrational properties, were computed and analysed using a CCSD(T) reference method since experimental data in this area are sparse or unknown. With the aim of investigating larger clusters, we explored several DFT functionals and basis sets able to mimic the reliable CCSD(T) approach. Among them, the PBE0/SBKJC+sp,d appears as the most efficient to describe the structural and vibrational properties since average differences of about 0.042Å and 5.1cm{sup −1} were obtained for bond lengths and fundamental vibrational frequencies, respectively for the first small clusters [1] of the series found from our GSAM method [2]. As further test, this model is used in order to investigate and revisit an experimental IR spectrum of Ga{sub n}As{sub m} mixture previously published by Li et al. [3]. More complicated is the difficulty which arises in the electronic description due to the presence of numerous low lying electronic states nearly degenerated to correctly describe the electronic structure. The case of Ga{sub 2}As will be discussed and the photoelectron spectra of the Ga{sub 2}As anion reanalyzed on the ground of our calculations [4] comparatively to the experimental spectra obtained by Neumark and co-workers [5].
Using density functional theory with the full-potential linearized augmented plane-wave method (FP-LAPW), we have study the structural, electronic, and magnetic properties of Ti{sub 2}FeZ (Z = Al, Ga, and In) alloys with Hg{sub 2}CuTi-type structure. The magnetic stabilities reveal that all our compounds exhibit ferrimagnetic (FiM) behaviors. The electronic structure report the existence of a gap energy equal to 0.56, 0.60, and 0.64 eV for Ti{sub 2}FeAl, Ti{sub 2}FeGa, and Ti{sub 2}FeIn, respectively, in the spin-down state and divulge metallic intersections at the Fermi level for the spin-up state. These results indicate that our compounds have a half-metallic (HM) nature. In addition to this, the total magnetic moments are in agreement with the obtained one by the Slater-Pauling rule (M{sub tot} = Z{sub tot} − 18), which indicates the 100% spin polarization for these compounds.
Graphical abstract: - Highlights: • A new type of phosphomolybdate K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) photocatalyst was successfully synthesized. • The products synthesized at 600 °C were mainly composed of nano-cubes. • The indirect band gap of K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) has been determined to be 2.93 eV. • K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) synthesized at 600 °C exhibits the highest photocatalytic activity. • The electronic structure was calculated by density functional calculations. - Abstract: A novel phosphomolybdate photocatalyst K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) has been successfully developed via a solid-state reaction. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), diffuse reflectance spectrum (DRS) and photoluminescence (PL) spectra. The photocatalytic activities of the samples prepared at different temperature were determined by the photooxidative decomposition of methylene blue (MB) in aqueous solution. The results revealed that K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) can be used as an effective photocatalyst under UV–vis irradiation and the nanocubes obtained at 600 °C exhibits the highest photocatalytic activity. The photodegradation of MB by K{sub 2}Bi(PO{sub 4})(MoO{sub 4}) nanocrystals followed the first-order kinetics. Theoretical calculations on electronic structure confirmed the indirect optical transitions property in the absorption edge region of K{sub 2}Bi(PO{sub 4})(MoO{sub 4}), and the orbital constitutions of CB and VB were also analyzed.
We present the Clenshaw–Curtis Spectral Quadrature (SQ) method for real-space O(N) Density Functional Theory (DFT) calculations. In this approach, all quantities of interest are expressed as bilinear forms or sums over bilinear forms, which are then approximated by spatially localized Clenshaw–Curtis quadrature rules. This technique is identically applicable to both insulating and metallic systems, and in conjunction with local reformulation of the electrostatics, enables the O(N) evaluation of the electronic density, energy, and atomic forces. The SQ approach also permits infinite-cell calculations without recourse to Brillouin zone integration or large supercells. We employ a finite difference representation in order to exploit the locality of electronic interactions in real space, enable systematic convergence, and facilitate large-scale parallel implementation. In particular, we derive expressions for the electronic density, total energy, and atomic forces that can be evaluated in O(N) operations. We demonstrate the systematic convergence of energies and forces with respect to quadrature order as well as truncation radius to the exact diagonalization result. In addition, we show convergence with respect to mesh size to established O(N 3 ) planewave results. In conclusion, we establish the efficiency of the proposed approach for high temperature calculations and discuss its particular suitability for large-scale parallel computation.
The band structure of β–LiGaO 2 is calculated using the quasiparticle self-consistent QSGWˆ method where the screened Coulomb interaction Wˆ is evaluated including electron-hole interaction ladder diagrams and G is the one-electron Green's function. Improved convergence compared to previous calculations leads to a significantly larger band gap of about 7.0 eV. However, exciton binding energies are found to be large and lead to an exciton gap of about 6.0 eV if also a zero-point-motion correction of about –0.4 eV is included. Furthermore, these results are in excellent agreement with recent experimental results on the onset of absorption. Besides the excitons observed thus far, the calculations indicate the existence of a Rydberg-like series of exciton excited states, which is however modified from the classical Wannier exciton model by the anisotropies of the material and the more complex mixing of Bloch states in the excitons resulting from the Bethe-Salpeter equation. The exciton fine structure and the exciton wave functions are visualized and analyzed in various ways.
Diamondoids are small diamond nanoparticles (NPs) that are built up from diamond cages. Unlike usual semiconductor NPs, their atomic structure is exactly known, thus they are ideal test-beds for benchmarking quantum chemical calculations. Their usage in spintronics and bioimaging applications requires a detailed knowledge of their electronic structure and optical properties. In this paper, we apply density functional theory (DFT) based methods to understand the electronic and optical properties of a few selected pure and modified diamondoids for which accurate experimental data exist. In particular, we use many-body perturbation theory methods, in the G{sub 0}W{sub 0} and G{sub 0}W{sub 0}+BSE approximations, and time-dependent DFT in the adiabatic local density approximation. We find large quasiparticle gap corrections that can exceed thrice the DFT gap. The electron-hole binding energy can be as large as 4 eV but it is considerably smaller than the GW corrections and thus G{sub 0}W{sub 0}+BSE optical gaps are about 50% larger than the Kohn-Sham (KS) DFT gaps. We find significant differences between KS time-dependent DFT and GW+BSE optical spectra on the selected diamondoids. The calculated G{sub 0}W{sub 0} quasiparticle levels agree well with the corresponding experimental vertical ionization energies. We show that nuclei dynamics in the ionization process can be significant and its contribution may reach about 0.5 eV in the adiabatic ionization energies.
Effect of chemical substitutions to the molecular structure of 3-hydroxy-picolinic acid on photo-switching properties of the system operating on excited-state intramolecular double proton transfer (d-ESIPT) process [M. F. Rode and A. L. Sobolewski, Chem. Phys. 409, 41 (2012)] was studied with the aid of electronic structure theory methods. It was shown that simultaneous application of electron-donating and electron-withdrawing substitutions at certain positions of the molecular frame increases the height of the S{sub 0}-state tautomerization barrier (ensuring thermal stability of isomers) and facilitates a barrierless access to the S{sub 1}/S{sub 0} conical intersection from the Franck-Condon region of the S{sub 1} potential-energy surface. Results of study point to the conclusion that the most challenging issue for practical design of a fast molecular photoswitch based on d-ESIPT phenomenon are to ensure a selectivity of optical excitation of a given tautomeric form of the system.
The electronic structure of BiVO{sub 4} has been studied by x-ray photoelectron, x-ray absorption, and x-ray emission spectroscopies, in comparison with density functional theory calculations. Our results confirm both the direct band gap of 2.48 eV and that the Bi 6s electrons hybridize with O 2p to form antibonding 'lone pair' states at the top of the valence band. The results highlight the suitability of combining s{sup 2} and d{sup 0} cations to produce photoactive ternary oxides.
Plane wave pseudopotential (PWP) density functional theory (DFT) calculation is the most widely used method for material simulations, but its absolute speed stagnated due to the inability to use large scale CPU based computers. By a drastic redesign of the algorithm, and moving all the major computation parts into GPU, we have reached a speed of 12 s per molecular dynamics (MD) step for a 512 atom system using 256 GPU cards. This is about 20 times faster than the CPU version of the code regardless of the number of CPU cores used. Our tests and analysis on different GPU platforms and configurations shed lights on the optimal GPU deployments for PWP-DFT calculations. An 1800 step MD simulation is used to study the liquid phase properties of GaInP.
Since the advent of the first computers, chemists have been at the forefront of using computers to understand and solve complex chemical problems. As the hardware and software have evolved, so have the theoretical and computational chemistry methods and algorithms. Parallel computers clearly changed the common computing paradigm in the late 1970s and 80s, and the field has again seen a paradigm shift with the advent of graphical processing units. This review explores the challenges and some of the solutions in transforming software from the terascale to the petascale and now to the upcoming exascale computers. While discussing the field in general, NWChem and its redesign, NWChemEx, will be highlighted as one of the early codesign projects to take advantage of massively parallel computers and emerging software standards to enable large scientific challenges to be tackled.
The primary focus of GAMESS over the last 5 years has been the development of new high-performance codes that are able to take effective and efficient advantage of the most advanced computer architectures, both CPU and accelerators. These efforts include employing density fitting and fragmentation methods to reduce the high scaling of well-correlated (e.g., coupled-cluster) methods as well as developing novel codes that can take optimal advantage of graphical processing units and other modern accelerators. Because accurate wave functions can be very complex, an important new functionality in GAMESS is the quasi-atomic orbital analysis, an unbiased approach to the understanding of covalent bonds embedded in the wave function. Finally, best practices for the maintenance and distribution of GAMESS are also discussed.
In this study, we introduce two simple tight-binding models, which we call fragment frontier orbital extrapolations (FFOE), to extrapolate important electronic properties to the polymer limit using electronic structure calculations on only a few small oligomers. In particular, we demonstrate by comparison to explicit density functional theory calculations that for long oligomers the energies of the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO), and of the first electronic excited state are accurately described as a function of number of repeat units by a simple effective Hamiltonian parameterized from electronic structure calculations on monomers, dimers and, optionally, tetramers. For the alternating copolymer materials that currently comprise some of the most efficient polymer organic photovoltaic devices one can use these simple but rigorous models to extrapolate computed properties to the polymer limit based on calculations on a small number of low-molecular-weight oligomers.
Symmetry adaptation, universality, and gate efficiency are central but often competing requirements in quantum algorithms for electronic structure and many-body physics. For example, fully symmetry-adapted universal operator pools typically generate long and deep quantum circuits; gate-efficient universal operator pools generally break symmetries; and gate-efficient, fully symmetry-adapted operator pools may not be universal. In this work, we analyze such symmetry dilemmas both theoretically and numerically. On the theory side, we prove that the popular, gate-efficient operator pool consisting of singlet spin-adapted singles and perfect-pairing doubles is not universal when spatial symmetry is enforced. To demonstrate the strengths and weaknesses of the three types of pools, we perform numerical simulations using an adaptive algorithm paired with operator pools that are (i) fully symmetry-adapted and universal, (ii) fully symmetry-adapted and non-universal, and (iii) breaking a single symmetry and universal. Our numerical simulations encompass three physically relevant scenarios in which the target state is (i) the global ground state, (ii) the ground state crossed by a state differing in multiple symmetry properties, and (iii) the ground state crossed by a state differing in a single symmetry property. Our results show when symmetry-breaking but universal pools can be used safely, when enforcing at least one distinguishing symmetry suffices, and when a particular symmetry must be rigorously preserved to avoid variational collapse. Together, the formal and numerical analyses provide a practical guide for designing and benchmarking symmetry-adapted operator pools that balance universality, resource requirements, and robust state targeting in quantum simulations for chemistry.