Structure and electronic properties and phase stabilities of the Cd(1-x)Zn(x)S solid solution in the range of 0≤x≤1

As an excellent bandgap-engineering material, the Cd(1-x)Zn(x)S solid solution, is found to be an efficient visible light response photocatalyst for water splitting, but few theoretical studies have been performed on it. A better characterization of the composition dependence of the physical and optical properties of this material and a thorough understanding of the bandgap-variation mechanism are necessary to optimize the design of high-efficience photocatalysts. In order to get an insight into these problems, we systematically investigated the crystal structure, the phase stability, and the electronic structures of the Cd(1-x)Zn(x)S solid solution by means of density functional theory calculations. The most energetically favorable arrangement of the Cd, Zn, S atoms and the structural disorder of the solid solution are revealed. The phase diagram of the Cd(1-x)Zn(x)S solid solution is calculated based on regular-solution model and compared with the experimental data. This is the first report on the calculated phase diagram of this solid solution, and can give guidance for the experimental synthesis of this material. Furthermore, the variation of the electronic structures versus x and its mechanism are elaborated in detail, and the experimental bandgap as a function of x is well predicted. Our findings provide important insights into the experimentally observed structural and electronic properties, and can give theoretical guidelines for the further design of the Cd(1-x)Zn(x)S solid solution.     

X-Ray spectra and electronic correlations of FeSe(1-x)Te(x)

Critical issues concerning emerging Fe-based superconductors include the degree of electron correlation and the origin of the superconductivity. X-Ray absorption spectra (XAS) and resonant inelastic X-ray scattering spectra (RIXS) of FeSe(1-x)Te(x) (x = 0-1) single crystals were obtained to study their electronic properties that relate to electron correlation and superconductivity. The linewidth of Fe L(2,3)-edges XAS of FeSe(1-x)Te(x) is narrower than that of Fe-pnictides, revealing the difference between their hybridization effects and localization character and those of other Fe-pnictides. While no significant differences exist between the Fe L-edge XAS and RIXS of FeSe(1-x)Te(x) and those of Fe-pnictides, Se K-edge and Te K-edge XAS exhibit substantial edge shift, suggesting that the superconductivity in an Fe-Se superconductor is strongly associated with the ligand states. A comparison of the Se K-edge and Te K-edge spectra reveals that the charge transfer may occur between Se and Te. Given the Coulomb interaction and the bandwidth, the spectral results indicate that FeSe(1-x)Te(x) is unlikely to be a weakly correlated system unlike the Fe-pnictides of the "1111" and "122" families. The spectral results further demonstrate that superconductivity in this class of Fe-based compounds is strongly associated with the ligand 4p hole state.     

Structure-property relationships of polyselenoethers [-(CH2)ySe-]x (y=1, 2, and 3) and related polyethers and polysulfides

Conformational characteristics, solution (melt) properties, and thermal properties of polyselenoethers [-(CH2)ySe-]x ( y=1, 2, and 3) have been revealed by the rotational isomeric state analysis of ab initio molecular orbital calculations and (1)H and (13)C NMR experiments for monomeric model compounds and compared with those of typical polyethers and polysulfides. The comparative results are summarized here as correlations in conformation among model compounds and unperturbed and crystalline states of the polymers, and thermal properties of the polymer crystals are discussed in terms of intramolecular and intermolecular interactions. By ab initio molecular orbital calculations under periodic boundary conditions, helical structures of poly(methylene oxide), poly(methylene sulfide), and poly(methylene selenide), and the crystal structure of poly(ethylene selenide) have been optimized, and their electronic structures have been predicted. A systematic methodology to predict and characterize up to higher-order structures and various physical properties of polymers incorporated in different phases has been attempted to be developed.     

One-pot noninjection synthesis of Cu-doped Zn(x)Cd(1-x)S nanocrystals with emission color tunable over entire visible spectrum

Unlike Mn doped quantum dots (d-dots), the emission color of Cu dopant in Cu d-dots is dependent on the nature, size, and composition of host nanocrystals (NCs). The tunable Cu dopant emission has been achieved via tuning the particle size of host NCs in previous reports. In this paper, for the first time we doped Cu impurity in Zn(x)Cd(1-x)S alloyed NCs and tuned the dopant emission in the whole visible spectrum via variation of the stoichiometric ratio of Zn/Cd precursors in the host Zn(x)Cd(1-x)S alloyed NCs. A facile noninjection and low cost approach for the synthesis of Cu:Zn(x)Cd(1-x)S d-dots was reported. The optical properties and structure of the obtained Cu:Zn(x)Cd(1-x)S d-dots have been characterized by UV-vis spectroscopy, photoluminescence (PL) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). The influences of various experimental variables, including Zn/Cd ratio, reaction temperature, and Cu dopant concentration, on the optical properties of Cu dopant emission have been systematically investigated. The as-prepared Cu:Zn(x)Cd(1-x)S d-dots did show PL emission but with quite low quantum yield (QY) (typically below 6%). With the deposition of ZnS shell around the Cu:Zn(x)Cd(1-x)S core NCs, the PL QY increased substantially with a maximum value of 65%. More importantly, the high PL QY can be preserved when the initial oil-soluble d-dots were transferred into aqueous media via ligand replacement by mercaptoundeconic acid. In addition, these d-dots have thermal stability up to 250 °C.     

Thermoelectric properties of Yb(x)Eu(1-x)Cd2Sb2

The thermoelectric performance of EuCd(2)Sb(2) and YbCd(2)Sb(2) was improved by mixed cation occupation. The composition, structure, and thermoelectric properties of Yb(x)Eu(1-x)Cd(2)Sb(2) (x=0, 0.5, 0.75, and 1) have been investigated. Polycrystalline samples are prepared by direct reaction of the elements. Thermoelectric properties were investigated after densification of the materials by spark plasma sintering. Yb(x)Eu(1-x)Cd(2)Sb(2) crystallizes in the P3m1 space group. The lattice parameters increase with the europium content. These materials show low electrical resistivity, high Seebeck coefficient, and low thermal conductivity together with high carrier concentration and high carrier mobility. ZT values of 0.88 and 0.97 are obtained for Yb(0.5)Eu(0.5)Cd(2)Sb(2) and Yb(0.75)Eu(0.25)Cd(2)Sb(2) at 650 K, respectively.     

First principles simulation of a superionic phase of hydrogen fluoride (HF) at high pressures and temperatures

We have conducted ab initio molecular dynamics simulations of hydrogen fluoride (HF) at pressures of 5-66 GPa along the 900 K isotherm. We predict a superionic phase at 33 GPa, where the fluorine atoms are fixed in a bcc lattice while the hydrogen atoms diffuse rapidly with a diffusion constant between 2 x 10(-5) and 5 x 10(-5)cm(2)s. We find that a transformation from asymmetric to symmetric hydrogen bonding occurs in HF at 66 GPa and 900 K. With superionic HF we have discovered a model system where symmetric hydrogen bonding occurs at experimentally achievable conditions. Given previous results on superionic H(2)O [Goldman et al., Phys. Rev. Lett. 94, 217801 (2005)] and NH(3) [Cavazzoni et al., Science 283, 44 (1999)], we conclude that high P, T superionic phases of electronegative element hydrides could be common.     

Organotellurium(VI) azides and halides

The reaction of azide with organotellurium(VI) halides Ph(5)TeBr and cis-(biphen)(2)TeF(2) (biphen = 2,2'-biphenyldiyl) resulted in the formation and isolation of Ph(5)TeN(3) (1) and cis-(biphen)(2)Te(N(3))(2) (2), which are the first tellurium(VI)-azide species. In addition to spectroscopic data, both crystal structures have been determined. Furthermore, the stability of possible Te(VI) species with higher azide contents Ph(x)()Te(N(3))(6)(-)(x)() and Me(x)()Te(N(3))(6)(-)(x)() as well as the syntheses and properties of their Ph/Me(x)()TeF(y)() precursors was investigated, including the crystal structure determination of trans-Ph(2)TeF(4) (3). Ab initio and density functional studies of all molecules regarding the structures and electronic populations were performed.     

New barium copper chalcogenides synthesized using two different chalcogen atoms: Ba2Cu(6-x)STe4 and Ba2Cu(6-x)Se(y)Te(5-y)

Ba(2)Cu(6-x)STe(4) and Ba(2)Cu(6-x)Se(y)Te(5-y) were prepared from the elements in stoichiometric ratios at 1123 K, followed by slow cooling. These chalcogenides are isostructural, adopting the space group Pbam (Z = 2), with lattice dimensions of a = 9.6560(6) ?, b = 14.0533(9) ?, c = 4.3524(3) ?, and V = 590.61(7) ?(3) in the case of Ba(2)Cu(5.53(3))STe(4). A significant phase width was observed in the case of Ba(2)Cu(6-x)Se(y)Te(5-y) with at least 0.17(3) ≤ x ≤ 0.57(4) and 0.48(1) ≤ y ≤ 1.92(4). The presence of either S or Se in addition to Te appears to be required for the formation of these materials. In the structure of Ba(2)Cu(6-x)STe(4), Cu-Te chains running along the c axis are interconnected via bridging S atoms to infinite layers parallel to the a,c plane. These layers alternate with the Ba atoms along the b axis. All Cu sites exhibit deficiencies of up to 26%. Depending on y in Ba(2)Cu(6-x)Se(y)Te(5-y), the bridging atom is either a Se atom or a Se/Te mixture when y ≤ 1, and the Te atoms of the Cu-Te chains are partially replaced by Se when y > 1. All atoms are in their most common oxidation states: Ba(2+), Cu(+), S(2-), Se(2-), and Te(2-). Without Cu deficiencies, these chalcogenides were computed to be small gap semiconductors; the Cu deficiencies lead to p-doped semiconducting properties, as experimentally observed on selected samples.     

Thermodynamic properties of ionic liquids-a cluster approach

We describe a method for calculating thermodynamic properties of ionic liquids by using standard quantum statistical thermodynamics as characterized by ab initio techniques. We review briefly how thermochemical properties for different sized clusters of ionic liquids are calculated by standard ab initio programs. The cluster partition functions allow one to calculate energies, enthalpies and Gibbs energies. Assuming that the ionic liquid exists exclusively as isolated ion-pairs in the gaseous phase and regarding the largest clusters as possible liquid structures, we could estimate vapor pressures, enthalpies of vaporization and entropies of vaporization. For possible boiling points it is shown how they vary with pressure.     

On the ideality of binary mixtures of ionic liquids

In this work, structural and dynamical properties of the binary mixture of 1-ethyl-3-methyl-imidazolium chloride and 1-ethyl-3-methyl-imidazolium thiocyanate are investigated from ab initio molecular dynamics simulations and compared to the pure ionic liquids. Furthermore, the binary mixture is simulated with two different densities to gain insight into how the selected density affects the different properties. In addition, a simple NMR experiment is carried out to investigate the changes of the chemical shifts of the hydrogen atoms due to the composition of the mixture.     

Raman spectra of ionic liquids: interpretation via computer simulation

Theoretical Raman spectra of the complex-forming ionic liquids LaCl3 and ScCl3, derived from molecular dynamics computer simulations, are presented. These simulations, which use polarizable ion interaction models, have previously been shown to predict structural properties in excellent agreement with diffraction experiments. The dependence of the polarizability of the melt on the ionic positions, which determines the Raman spectrum through the time dependence of the polarizability correlation function, is modeled on the basis of ab initio electronic structure calculations carried out on alkali chlorides. New simulation techniques are introduced in order to allow the spectrum to be calculated with acceptable statistics. The calculated spectra are in semiquantitative agreement with experimental data. The distinctive bands which appear in the spectra of such complex melts are linked to the vibrations of the transient coordination complexes which form in these melts and new interpretations for the origin of several well-known features are proposed. The simulations thus enable a link between the structure of a melt as perceived through Raman spectroscopy and through diffraction experiments to be made.     

Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xH(x-1)]-

We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine-acetic acid mixtures. The simple 1 : 1 acid-base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)(x)H(x-1)](-) stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1 : 1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion.     

Photoluminescence and Raman scattering from catalytically grown Zn(x)Cd(1-x)Se alloy nanowires

Zn(x)Cd(1-x)Se alloy nanowires, with composition x = 0, 0.2, 0.5, 0.7, and 1, have been successfully synthesized by a chemical vapor deposition (CVD) method assisted with laser ablation. The as-synthesized alloy nanowires, 60-150 nm in diameter and several tens of micrometers in length, complied with a typical vapor-liquid-solid (VLS) growth mechanism. The Zn(x)Cd(1-x)Se nanowires are single crystalline revealed from high-resolution transmission electron microscopic (HRTEM) images, selected area electron diffraction (SAED) patterns, and X-ray diffraction (XRD) measurement. Compositions of the alloy nanowires can be adjusted by varying the precursor ratios of the laser ablated target and the CVD deposition temperature. Crystalline structures of the Zn(x)Cd(1-x)Se nanowires are hexagonal wurtzite at x = 0, 0.2, and 0.5 with the [0 1 -1 0] growth direction and zinc blende at x = 0.7 and 1 with the [1 -1 1] growth direction. Energy gaps of the Zn(x)Cd(1-x)Se nanowires, determined from micro-photoluminescence (PL) measurements, change nonlinearly as a quadratic function of x with a bowing parameter of approximately 0.45 eV. Strong PL from the Zn(x)Cd(1-x)Se nanowires can be tuned from red (712 nm) to blue (463 nm) with x varying from 0 to 1 and has demonstrated that the alloy nanowires have potential applications in optical and sensory nanotechnology. Micro-Raman shifts of the longitudinal optical (LO) phonon mode observed in the Zn(x)Cd(1-x)Se nanowires show a one-mode behavior pattern following the prediction of a modified random element isodisplacement (MREI) model.     

Characterizing the nature of virtual amorphous silicon

Virtual samples of approximations to real amorphous silicon, a-Si, have been prepared using several different processing routes. These include a fast quench from the melt followed by a long slow annealing period using molecular dynamics, a Reverse Monte Carlo approach, and an ab initio minimization. The characterization of these virtual a-Si samples includes a consideration of structural data (the radial distribution function, angular order, etc.), electronic properties (through the density of states), and thermodynamic information (chiefly the nature of the phase transformation from a-Si to liquid). The properties of a-Si are compared to network models, via the continuous random network model, and to experiment. We investigated the stability of virtual a-Si and consider its implications for use in future simulation studies. We have demonstrated the necessity for the accuracy provided by ab initio-based models to describe the interatomic potentials. Throughout this study, we have monitored the role of order in determining physical properties, as characterized by traditional routes (such as angular correlations) and more novel ones (the signature cell method).     

Structure of liquid water at ambient temperature from ab initio molecular dynamics performed in the complete basis set limit

Structural properties of liquid water at ambient temperature were studied using Car-Parrinello [Phys. Rev. Lett. 55, 2471 (1985)] ab initio molecular dynamics (CPAIMD) simulations combined with the Kohn-Sham (KS) density functional theory and the BLYP exchange-correlation functional for the electronic structure. Unlike other recent work on the same subject, where plane-wave (PW) or hybrid Gaussian/plane-wave basis sets were employed, in the present paper, a discrete variable representation (DVR) basis set is used to expand the KS orbitals, so that with the real-space grid adapted in the present work, the properties of liquid water could be obtained very near the complete basis set limit. Structural properties of liquid water were extracted from a 30 ps CPAIMD-BLYP/DVR trajectory at 300 K. The radial distribution functions (RDFs), spatial distribution functions, and hydrogen bond geometry obtained from the CPAIMD-BLYP/DVR simulation are generally in good agreement with the most up to date experimental measurements. Compared to recent ab initio MD simulations based on PW basis sets, less significant overstructuring was found in the RDFs and the distributions of hydrogen bond angles, suggesting that previous plane-wave and Gaussian basis set calculations have exaggerated the tendency toward overstructuring.     

Calculating geochemical reaction pathways--exploration of the inner-sphere water exchange mechanism in Al(H2O)6(3+)(aq) + nH2O with ab Initio calculations and molecular dynamics

We have simulated exchange of inner-sphere and bulk water molecules for different sizes of Al3+(aq) clusters, Al(H2O)63+ + nH2O for n = 0, 1, 6, or 12, with ab initio and molecular dynamics simulations, in order to understand how robust the ab initio method is for identifying hydrolytic reaction pathways of particular importance to geochemistry. In contrast to many interfacial reactions, this particular elementary reaction is particularly simple and well-constrained by experiment. Nevertheless, we find that a rich array of parallel reaction pathways depend sensitively on the details of the solvation sphere and structure and that larger clusters are not necessarily better. Inner-sphere water exchange in Al3+(aq) may occur through two Langford-Gray dissociative pathways, one in which the incoming and outgoing waters are cis, the other in which they are trans to one another. A large majority of exchanges in the molecular dynamics simulations occurred via the trans mechanism, in contrast to the predictions of the ab initio method. In Al(H2O)63+ + H2O, the cis mechanism has a transition state of 84.3 kJ/mol, which is in good agreement with previous experimental and ab initio results, while the trans mechanism has only a saddle point with two negative frequencies, not a transition state, at 89.7 kJ/mol. In addition to the exchange mechanisms, dissociation pathways could be identified that were considerably lower in energy than experiment and varied considerably between 60 and 100 kJ/mol, depending on the particular geometry and cluster size, with no clear relation between the two. Ab initio calculations using large clusters with full second coordination spheres (n = 12) were unable to find dissociation or exchange transition states because the network of hydrogen bonds in the second coordination sphere was too rigid to accommodate the outgoing inner-sphere water. Our results indicate that caution should surround ab initio simulation of complicated dynamic processes such as hydrolysis, ion exchange, and interfacial reactions that involve several steps. Dynamic methods of simulation need to accompany static methods such as ab initio calculation, and it is best to consider simulated pathways as hypotheses to be tested experimentally rather than definitive properties of the reaction.     

Accuracy of existing atomic potentials for the CdTe semiconductor compound

CdTe and CdTe-based Cd(1-x)Zn(x)Te (CZT) alloys are important semiconductor compounds that are used in a variety of technologies including solar cells, radiation detectors, and medical imaging devices. Performance of such systems, however, is limited due to the propensity of nano- and micro-scale defects that form during crystal growth and manufacturing processes. Molecular dynamics simulations offer an effective approach to study the formation and interaction of atomic scale defects in these crystals, and provide insight on how to minimize their concentrations. The success of such a modeling effort relies on the accuracy and transferability of the underlying interatomic potential used in simulations. Such a potential must not only predict a correct trend of structures and energies of a variety of elemental and compound lattices, defects, and surfaces but also capture correct melting behavior and should be capable of simulating crystalline growth during vapor deposition as these processes sample a variety of local configurations. In this paper, we perform a detailed evaluation of the performance of two literature potentials for CdTe, one having the Stillinger-Weber form and the other possessing the Tersoff form. We examine simulations of structures and the corresponding energies of a variety of elemental and compound lattices, defects, and surfaces compared to those obtained from ab initio calculations and experiments. We also perform melting temperature calculations and vapor deposition simulations. Our calculations show that the Stillinger-Weber parameterization produces the correct lowest energy structure. This potential, however, is not sufficiently transferrable for defect studies. Origins of the problems of these potentials are discussed and insights leading to the development of a more transferrable potential suitable for molecular dynamics simulations of defects in CdTe crystals are provided.     

Lithium solvation in bis(trifluoromethanesulfonyl)imide-based ionic liquids

The lithium solvation in (1 -x)(EMI-TFSI), xLiTFSI ionic liquids where EMI(+) is the 1-ethyl-3-methylimidazolium cation and TFSI(-) the bis(trifluoromethanesulfonyl)imide anion, is shown by Raman spectroscopy to involve essentially [Li(TFSI)(2)](-) anionic clusters for 0 < x < 0.4, but addition of stoichiometric amounts of solvents S such as oligoethers changes the lithium solvation into [Li(S)(m)](+) cationic clusters; the lithium transference number in TFSI-based ionic liquid electrolytes for lithium batteries should thus be strongly improved.