Number Of Atoms Research Articles

Structural Characteristics, Electronic Properties, and Coupling Behavior of 12-4-12, 12-3-12, 12-2-12 Cationic Surfactants: A First-Principles Computational Investigation and Experimental Raman Spectroscopy

In this study, we present a comprehensive first-principles computational investigation focused on the structural characteristics, electronic properties, and coupling integrations of three cationic Gemini surfactants: 12-4-12, 12-3-12, and 12-2-12 ((CH3(CH2)11)(CH3)2-N+-(CH2)n-N+(CH3(CH2)11)(CH3)2, where n = 2, 3, or 4). By employing Density Functional Theory (DFT) computations, we aimed to gain insights into the fundamental aspects of these surfactant molecules, and the intermolecular interactions among these surfactant molecules. We examined different conformers of each surfactant, including parallel, wing, and bent conformers, and compared their relative stability and properties. We elucidated that the complex structural characteristics, electronic properties, and molecular arrangements of the surfactants vary according to the number of carbon atoms in the central spacer. We also conducted experimental Raman spectroscopy on the three surfactants to compare the results with our computational findings. Furthermore, we computed the coupling behaviors of different conformers of 12-4-12 surfactants in order to gain insights into their coupling mechanism.

Study on thermodynamic parameters of volatile components in polydimethylsiloxane and polystyrene

In polymer production, devolatilization is an important unit operation that separates low molecular weight components from the polymer system. The presence of volatile matter not only reduces the quality of the product, but may also cause harm to users and the environment. The Henry’s coefficient is the most fundamental parameter in the vapor–liquid equilibrium relationship. The Henry’s coefficient of n-pentane, n-hexane, and n-octane for polydimethyl siloxane (PDMS) and polystyrene (PS) were measured using the pressure difference method. The influence of different operating conditions on Henry’s coefficient has been studied. The results indicate that as the experimental temperature increases, the Henry’s coefficient of volatile matter gradually increases. The viscosity of polymers has little effect on the Henry’s coefficient. Under the same volatile matter conditions, when the viscosity increases from 50 cst to 5000 cst, the maximum growth rate of the Henry’s coefficient is only 5%. As the number of carbon atoms increases, the Henry’s coefficient decreases. This work provides theoretical guidance for polymer devolatilization processes in industry.

Physical mechanism underlying the enhancement effect of carbon in heavily phosphorus-doped Czochralski silicon substrate on phosphorus out-diffusion within n/n+ epitaxial wafer

The effects of carbon in heavily phosphorus-doped Czochralski (HP-Cz) silicon (Si) substrates, with the concentrations across an order of magnitude from 1016 to 1017 cm−3, on the out-diffusion of phosphorus impurities within n/n+ epitaxial Si (Epi-Si) wafers have been investigated. It is found that the increase in the carbon concentration ([C]) from 1.0 × 1016 to 1.0 × 1017 cm−3 leads to the enhanced phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1100 °C in an N2 or an O2 ambient or to anneal at 1150 °C in an N2 ambient, but hardly affects the phosphorus out-diffusion within the n/n+ Epi-Si wafer when subjected to anneal at 1150 °C in an O2 ambient. Based on the density functional theory calculations, it is derived that the increase in the [C] from 1.0 × 1016 to 1.0 × 1017 cm−3 in the HP-Cz Si substrate results in a significantly increased thermal equilibrium concentration of self-interstitial silicon (SiI) atoms at 1100 or 1150 °C, which, in turn, leads to the increased concentration of the SiI atoms that out-diffuse from the substrate to the epitaxial layer because the SiI atoms diffuse extremely fast in Si. Such a carbon-induced increase in the concentration of SiI atoms is believed to be responsible for the aforementioned enhanced phosphorus out-diffusion, which is predominantly dictated by the interstitialcy mechanism. In the case of anneal in the O2 ambient at sufficiently high temperatures such as 1150 °C, a large number of excessive SiI atoms injected into the Epi-Si wafer substantially mask the carbon enhancement effect on the phosphorus out-diffusion. Of technological significance, it is deduced that the [C] should be not higher than 1.0 × 1016 cm−3 in the HP-Cz Si wafers as the substrates of n/n+ Epi-Si wafers used for power devices.

Spatial calibration of high-density absorption imaging

The accurate determination of atom numbers is an ubiquitous problem in the field of ultracold atoms. For modest atom numbers, absolute calibration techniques are available, however, for large numbers and high densities, the available techniques neglect many-body scattering processes. Here, a spatial calibration technique for time-of-flight absorption images of ultracold atomic clouds is presented. The calibration is obtained from radially averaged absorption images and we provide a practical guide to the calibration process. It is shown that the calibration coefficient scales linearly with optical density and depends on the absorbed photon number for the experimental conditions explored here. This allows for the direct inclusion of a spatially dependent calibration in the image analysis. For typical ultracold atom clouds the spatial calibration technique leads to corrections in the detected atom number up to ≈12% and temperature up to ≈14% in comparison to previous calibration techniques. The technique presented here addresses a major difficulty in absorption imaging of ultracold atomic clouds and prompts further theoretical work to understand the scattering processes in ultracold dense clouds of atoms for accurate atom number calibration.

Descriptors-based machine-learning prediction of cetane number using quantitative structure–property relationship

The physicochemical properties of liquid alternative fuels are important but difficult to measure/predict, especially when complex surrogate fuels are concerned. In the present work, machine learning is used to develop quantitative structure–property relationship models. The fuel chemical structure is represented by molecular descriptors, allowing the linking of important features of the fuel composition and key properties of fuel utilization. Feature selection is employed to select the most relevant features that describe the chemical structure of the fuel and several machine learning algorithms are tested to construct interpretable models. The effectiveness of the methodology is demonstrated through the development of accurate and interpretable predictive models for cetane numbers, with a focus on understanding the link between molecular structure and fuel properties. In this context, matrix-based descriptors and descriptors related to the number of atoms in the molecule are directly linked with the cetane number of hydrocarbons. Furthermore, the results showed that molecular connectivity indices play a role in the cetane number for aromatic molecules. Also, the methodology is extended to predict the cetane number of ester and ether molecules, leveraging the design of alternative fuels towards fully sustainable fuel utilization.

Mechanical and surface characteristics in laser-assisted machining of NiFeCr alloy: An atomic-scale understanding

This investigation explores mechanical characteristics and subsurface damage of NiFeCr alloy in laser-assisted machining through molecular dynamics simulation. The results of machining force, friction coefficient, local strain/stress, temperature distribution, subsurface damage, surface morphology, and worn volume are comprehensively explored, thereby revealing the mechanism of laser-assisted machining under different working conditions. Compared to conventional processing, average machining force, shear strain, subsurface damage, and dislocated length are all reduced in laser-assisted machining, which improves surface finish quality. Amorphization of removed chips in laser-assisted machining enhances the material removal efficiency. Analysis of various laser powers shows a decreased machining force with increasing laser power. However, residual stress and temperature rise, potentially impacting surface integrity. The subsurface damage depth exhibits nonlinearity with increasing laser energy, highlighting the competition between mechanical stress and thermal effect. The surface morphology and atomic flow demonstrate effective material removal with increasing laser power. The average machining force, friction coefficient, and subsurface damage depth show nonlinear relationships with cutting speed. The number of worn atoms is proportional to machining length and cutting speed, indicating enhanced material removal during high-speed machining.

Geometries, electronic structures, mechanical properties and stabilities of Fe128Hen and Fe127VacHen: An uniaxial compression effect

Owning to the factors of external mechanical loads and high heat flux deposition, various degrees of strain or stress are inevitably introduced into the structural materials of nuclear fusion reactors. The uniaxial compression effects on the geometries, electronic structures, mechanical properties, and stabilities of Fe128Hen and Fe127VacHen were studied by first-principles calculations in this work. The results show that the lattice suffers from a noticeable inclination or disorder as the strain reaches 15%. The maximum stress of the stress–strain curves implied that the mechanical characteristics decay considerably as the number of He atoms increases, but the presence of a vacancy mitigated this effect. Compressive strain decreases the stability of Fe atom in the perfect pure Fe system, but it slightly elevates the monovacancy formation energy from Fe128He3 onward. According to the binding energy of He-He, compressive strain enhanced the aggregation of He. The migration barriers of an interstitial He atom exhibit anisotropy under uniaxial compressive strain, which was explained by the variations of the surrounding architectures.

Assessing the matrix effects on MALDI-MS in the positive and negative ion mode detection for protein-protected metal nanoclusters

Protein-protected metal nanoclusters (MNCs) represent a new class of highly photoluminescent nanomaterials that have wide applications. Suitable reaction conditions combining protein and metal precursors can produce a vast range of different NC sizes (i.e. different number of metal atoms). The average number of metal atoms per protein can be determined by mass spectrometry (MS). MS coupled with matrix-assisted laser desorption ionization (MALDI) presents a number of advantages such as detection with high sensitivity of nanoclusters with high molecular weights. Although many protein-protected MNCs have been characterized by MALDI-MS, a large dispersion in the number of metal atoms has been reported mainly due to sample preparation. In this work, we optimized the protocols for negative and positive ion detection mode as a general MALDI-MS sample preparation method for protein-protected MNCs (bovine serum albumin and lysozyme and with gold and silver). Negative and positive ion mode detection was compared, showing that negative ion mode detection in MALDI-MS can also be used with acidic matrices. Obvious matrix effects on ion signals and peak positions by MALDI-MS were observed. The average metal numbers of MNCs embedded in proteins are different depending on the MALDI matrix. The matrix effects give a warning for more serious consideration on MALDI-MS measurement and spectra analysis of MNCs.

The Truncated Moment Problem on Reducible Cubic Curves I: Parabolic and Circular Type Relations

In this article we study the bivariate truncated moment problem (TMP) of degree 2k on reducible cubic curves. First we show that every such TMP is equivalent after applying an affine linear transformation to one of 8 canonical forms of the curve. The case of the union of three parallel lines was solved in Zalar (Linear Algebra Appl 649:186–239, 2022. https://doi.org/10.1016/j.laa.2022.05.008), while the degree 6 cases in Yoo (Integral Equ Oper Theory 88:45–63, 2017). Second we characterize in terms of concrete numerical conditions the existence of the solution to the TMP on two of the remaining cases concretely, i.e., a union of a line and a circle y(ay+x2+y2)=0,a∈R\\{0}\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$y(ay+x^2+y^2)=0, a\\in {\\mathbb {R}}{\\setminus } \\{0\\}$$\\end{document}, and a union of a line and a parabola y(x-y2)=0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$y(x-y^2)=0$$\\end{document}. In both cases we also determine the number of atoms in a minimal representing measure.

ScaleLat: A chemical structure matching algorithm for mapping atomic structure of multi-phase system and high entropy alloys

ScaleLat (Scale Lattice) is a computer program written in C for performing the atomic structure analysis of multi-phase system or high entropy alloys (HEAs). The program implements an atomic cluster cell extraction algorithm to obtain all symmetry independent characteristic atomic cluster cells for the complex atomic configurations which are usually obtained from molecular dynamics or kinetic Monte-Carlo simulations at nanoscale or mesoscopic scale. ScaleLat implements an efficient and unique chemical structure matching algorithm to match all extracted atomic clusters from a large supercell (>104 atoms) to a representative small one (∼ 103 or less), providing the possibility to directly use the highly accurate quantum mechanical methods to study the electronic, magnetic, and mechanical properties of multi-component alloys for complex microstructures. We demonstrate the capability of ScaleLat code by conducting both the atomic structure matching analysis for Fe-12.8 at.% Cr binary alloy and equiatomic CrFeCoNiCu high entropy alloy, successfully obtaining the representative supercells containing 102∼103 atoms for two systems. The reliability of the proposed chemical structure matching scheme is tested and confirmed by calculating the electronic structures of both examples using trial supercells with various sizes. Overall, ScaleLat program provides a universal platform to efficiently map all essential chemical structures of large complex atomic structures to a relatively easy-handling small supercell for quantum mechanical calculations of various user interested properties. Program SummaryProgram Title: ScaleLatCPC Library link to program files: https://doi.org/10.17632/cv6wsxy938.1Developer's repository link: https://github.com/NanLi-xjtu/ScaleLat.gitLicensing provisions: MITProgramming language: CNature of Problem: Very large supercells containing more than 104 atoms must be used to describe the atomic structure of multi-phase materials or high entropy alloys, and their electronic and mechanical properties are almost not possible to be investigated using quantum mechanical calculations within conventional computational hardware. Decreasing the total number of atoms in a smaller representative supercell which preserves all essential chemical structures of the original large supercell is the key to tackling the problem.Solution to the Problem: An atomic cluster cell extraction algorithm is realized to thoroughly obtain all symmetry independent characteristic chemical structures of multi-phase system or high entropy alloys. Utilizing the direct atom swapping method, the efficient chemical structure matching procedure is developed to map all extracted characteristic atomic cluster cells of benchmark structure to the small supercell by minimizing their differences in both the types and relative fractions of atomic cluster cell sets.

Investigation of infra-red spectra of three chiral liquid crystalline compounds with different fluorosubstitution of benzene ring

The IR spectra of three liquid crystalline compounds, differing only by the number of fluorine atoms in the molecular core, are investigated. The DFT+D3/BLYP-def2SVP calculations for isolated molecules are applied for the band assignments of the experimental IR spectra collected in the crystal phase. Additional DFT calculations, including the B3LYP exchange-correlation functional and def2TZVPP basis set, are also performed for the compound without the fluorine atoms in the molecular core. The scaling factors between the experimental and calculated peak positions, obtained at different levels of theory, are compared. For all compounds, the absorption bands assigned to the C=O stretching vibrations are analyzed as a function of temperature in the isotropic liquid, smectic phases, and crystal phase. The formation of hydrogen bonding involving the C=O groups during crystallization is inferred. The differences in the crystallization temperature of three compounds and the presence of the hexatic smectic phase for only one compound are discussed.

Soft solution state and hard aging state of Inconel 718 reached via optimized precipitation elements using cluster formula approach

The superior high-temperature performance of Inconel 718 is originated mainly from the precipitation strengthening via Nb, Al, and Ti alloying. Inappropriate contents of the precipitation elements may lead to over-strengthened solution state and insufficiently strengthened aging state. We have previously identified the alloy composition formula [(Nb,Al,Ti)1-(Ni,Fe,Cr,Mo)12](Ni,Fe,Cr,Mo)5 using the cluster formula approach, where the 18-atom structural unit is composed of a nearest-neighbor cluster, centered by one precipitation elements, plus five glue atoms situated at the next neighbors. On the basis of this formula, the present work designs a series of alloys using (Nb,Al,Ti) = 0.93, 1, and 1.06, with 4.9 and 5.5 wt % Nb, 0.68 and 0.5 wt % Al, and 1.10 wt% Ti corresponding to the upper-to-middle ranges in the ASTM standard. In particular, when the total number of atoms in the formula is equal to one, (Nb0.6Al0.2Ti0.2), the alloy is soft at the solution state (σUTS = 825 MPa < 965 MPa of the standard and EL = 70.3 % > 30 %) and reaches high strength levels after aging (σUTS = 1400 MPa > 1240 MPa and EL = 23.4 % > 12 % at room temperature, σUTS = 1100 MPa > 965 MPa and EL = 10.2 % > 5 % at 923 K). This alloy also shows the lowest coarsening rate of 4–7 × 10−3 nm3 s−1 after long-term aging at 923 K, lower than the prevailing coarsening rate of about 16 × 10−3 nm3 s−1.

Design and synthesis of 6-C-alkyl-DMDP type nanomolar inhibitors of β-galactosidase and β-glucosidase based on broussonetine S and related derivatives

Broussonetine S (9), its C-1′ and C-10′ stereoisomers, and their corresponding enantiomers have been synthesized from enantiomeric arabinose-derived cyclic nitrones, with cross metathesis (CM), epoxidation and Keck asymmetric allylation as key steps. Glycosidase inhibition assays showed that broussonetine S (9) and its C-10′ epimer (10′-epi-9) were nanomolar inhibitors of bovine liver β-galactosidase and β-glucosidase; while their C-1′ stereoisomers were 10-fold less potent towards these enzymes. The glycosidase inhibition results and molecular docking calculations revealed the importance of the configurations of pyrrolidine core and C-1′ hydroxyl for inhibition potency and spectra. Together with the docking calculations we previously reported for α-1-C-alkyl-DAB derivatives, we designed and synthesized a series of 6-C-alkyl-DMDP derivatives with very simple alkyl chains. The inhibition potency of these derivatives was enhanced by increasing the length of the side chain, and maintained at nanomolar scale inhibitions of bovine liver β-glucosidase and β-galactosidase after the alkyl groups are longer than eight or ten carbons for the (6R)-C-alkyl-DMDP derivatives and their 6S epimers, respectively. Molecular docking calculations indicated that each series of 6-C-alkyl-DMDP derivatives resides in the same active site of β-glucosidase or β-galactosidase with basically similar binding conformations, and their C-6 long alkyl chains extend outwards along the hydrophobic groove with similar orientations. The increasing inhibitions of β-glucosidase and β-galactosidase with the number of carbon atoms in the side chains may be explained by improved adaptability of longer alkyl chains in the hydrophobic grooves. In addition, the lower β-glucosidase and β-galactosidase inhibitions of (6S)-C-alkyl-DMDP derivatives than their C-6 R stereoisomers can be attributed to the misfolding of their alkyl chains and resulted decreased adaptability in the hydrophobic groove. The work reported herein is valuable for design and development of more potent and selective inhibitors of β-galactosidase and β-glucosidase, which have potential in treatment of lysosomal storage diseases. Furthermore, part of the 6-C-alkyl-DMDP derivatives and their enantiomers were also tested as potential anti-cancer agents; all the compounds tested were found with moderate cytotoxic effects on MKN45 cells, which would indicate potential applications of these iminosugars in development of novel anticancer agents.

Control of Multi-Fluorination Number and Position in D-π-A Type Polymers and Their Impact on High-Voltage Organic Photovoltaics.

Exploring the structure-performance relationship of high-voltage organic solar cells (OSCs) is significant for pushing material design and promoting photovoltaic performance. Herein, we chose a D-π-A type polymer composed of 4,8-bis(thiophene-2-yl)-benzo[1,2-b:4,5-b']dithiophene (BDT-T) and benzotriazole (BTA) units as the benchmark to investigate the effect of the fluorination number and position of the polymers on the device performance of the high-voltage OSCs, with a benzotriazole-based small molecule (BTA3) as the acceptor. F00, F20, and F40 are the polymers with progressively increasing F atoms on the D units, while F02, F22, and F42 are the polymers with further attachment of F atoms to the BTA units based on the above three polymers. Fluorination positively affects the molecular planarity, dipole moment, and molecular aggregations. Our results show that VOC increases with the number of fluorine atoms, and fluorination on the D units has a greater effect on VOC than on the A unit. F42 with six fluorine atom substitutions achieves the highest VOC (1.23 V). When four F atoms are located on the D units, the short-circuit current (JSC) and fill factor (FF) plummet, and before that, they remain almost constant. The drop in JSC and FF in F40- and F42-based devices may be attributed to inefficient charge transfer and severe charge recombination. The F22:BTA3 system achieves the highest power conversion efficiency of 9.5% with a VOC of 1.20 V due to the excellent balance between the photovoltaic parameters. Our study provides insights for the future application of fluorination strategies in molecular design for high-voltage organic photovoltaics.

First Principle Study on Structural, Electronic, Magnetic, and Optical Properties of Co-Doped Middle Size Silver Clusters.

The structural, electronic, magnetic, and optical properties of Co-doped 10-20-atom silver clusters are investigated by GGA/PBE via the density functional theory. The Ag-Co clusters form core-shell structures with a Co atom in the center. Co atom doping modulates electronic properties like energy gap, molecular softness, global hardness, electronegativity, and electrophilicity index. For the optical spectra of the Ag-Co clusters, the energy of their spectra overall exhibits little change with increasing numbers of atoms; the strongest peaks are roughly distributed at 3.5 eV, and the intensity of their spectra overall is strengthened. Raman and vibrational spectra reflect structural changes with Co atom addition. The addition of the Co atom alters magnetic moments of specific Ag-Co clusters, while others remain unchanged.

Effects of chemical action of polishing medium on the material removal of SiC

The chemical action mechanism in the chemical mechanical polishing of SiC substrate remains elusive, which has great limitations on the selection of polishing solution and polishing parameters. In this paper, the cutting process of unreacted SiC (U–SiC) and the SiC reacted with H2O (R-SiC-H2O) and H2O2 (R-SiC-H2O2) was studied with an individual diamond abrasive particle by molecular dynamics simulation. The influence of chemical reaction and cutting speed on the material removal of SiC was explored by focusing on the removal rate, surface quality, machining temperature and machining stress. The simulation results showed that the number of removed atoms increased, and the surface roughness and subsurface damage depth decreased for SiC at the same cutting speed after the chemical action. Although the number of removal atoms increased with the increase of cutting speed, the surface roughness and subsurface damage depth increased at the same time. The effects of the polishing medium on the material removal process for SiC can be attributed to the decrease of surface hardness and Si–C bonding energy after the reaction of the polishing medium and SiC. The results provide a guidance for the selection of chemical mechanical polishing systems and machining parameters.

Bose-Einstein Condensation by Polarization Gradient Laser Cooling.

Attempts to create quantum degenerate gases without evaporative cooling have been pursued since the early days of laser cooling, with the consensus that polarization gradient cooling (PGC, also known as "optical molasses") alone cannot reach condensation. In the present work, we report that simple PGC can generate a small Bose-Einstein condensate (BEC) inside a corrugated micrometer-sized optical dipole trap. The experimental parameters enabling BEC creation were found by machine learning, which increased the atom number by a factor of 5 and decreased the temperature by a factor of 2.5, corresponding to almost 2 orders of magnitude gain in phase space density. When the trapping light is slightly misaligned through a microscopic objective lens, a BEC of ∼250 ^{87}Rb atoms is formed inside a local dimple within 40ms of PGC after MOT loading.

Crystal chemistry and ionic conductivity of garnet-type solid-state electrolyte, Li5-xLa3(NbTa)O12-y

Crystal structures, microtopography, morphologies, elemental compositions, and ionic conductivity have been investigated for Li5-xLa3(Nb,Ta)O12-y using X-ray diffraction (XRD), field-emission analytical scanning and transmission electron microscopies (S/TEM), and electrochemical impedance spectroscopy. Using Rietveld refinements with powder XRD patterns, we determined that the number of Li atoms in the formula is less than 5 and that Li5-xLa3(NbTa)O12-y crystallizes in the cubic garnet structure with a space group Ia-3d. Sintering at varying temperatures (750–1000 °C) for 5 h in an ambient atmosphere produced distinct outcomes. Rietveld refinements disclosed that the sample sintered at 1000 °C (Li3.43(2)La3Nb1.07(2)Ta0.93(2)O12-y, a = 12.8361(7) Å, V = 2114.96(3) Å3) exhibited the highest ionic conductivity, while the 850 °C sample had the lowest conductivity, characterized by lower Li concentration and impurity phases (Li(Nb,Ta)3O88, Li2CO3). Analyses, including XRD and electron microscopy, confirmed the 1000 °C sample as a relatively phase pure with enhanced Li content (Li/La = 1.2), larger grains (15 μm), and uniform crystallinity. The 1000 °C sample introduced additional partially filled Li3 (96h) sites, promoting Li migration, and enhancing ionic conductivity. The resulting XRD pattern at 1000 °C has been submitted to the Powder Diffraction File as a reference.

Clogauite, PbBi4Te4S3, a new member of the aleksite series

AbstractClogauite, ideally PbBi4Te4S3 is the new n = 1 member of the aleksite series, PbnBi4Te4Sn+2, where n is the homologue number. Clogauite is named from the type locality, the Clogau gold mine, Dolgellau Gold belt, Gwynedd, North Wales, United Kingdom. The mineral and name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2023–062). The aleksite series is an accretional homologous series in which each member is derived from the same 5-atom tetradymite archetype. Clogauite crystallises in the trigonal crystal system (space group: P$\bar{3}$m1, #164). Three distinct polytypes of clogauite are recognised, corresponding to identical chemistry but different layer sequences, expressed as (57), (5559) and (557.559), respectively, in reference to the number of atoms in individual layer sequences. These are clogauite-12H, a = 4.277(4) Å, c = 23.46(14) Å, V = 371.598 Å3 and Z = 1; clogauite-24H, a = 4.278(4) Å, c = 46.88(31) Å, V = 743.053 Å3 and Z = 2; and clogauite-36H, a = 4.278(4) Å, c = 70.36(32) Å, V = 1115.283 Å3 and Z = 3. Clogauite is opaque, with a pale grey colour in reflected light. Reflectance is higher than tetradymite or galena. Bireflectance and anisotropy are strong. Structural data were determined from measurement of atomic-scale HAADF STEM imaging showing the internal arrangement of component atoms and characteristic selected area electron diffraction patterns for each polytype. The structures were then further constrained from ab initio total energy calculations and structure relaxation using density functional theory (DFT) using the measured parameters as input data. The relaxed crystal structure for each polytype was modelled to generate crystallographic information files (cif). STEM and electron diffraction simulations based on the crystallographic information data obtained from the DFT calculations show an excellent match to the empirical measurements.

Modeling the electroluminescence of atomic wires from quantum dynamics simulations.

Static and time-dependent quantum-mechanical approaches have been employed in the literature to characterize the physics of light-emitting molecules and nanostructures. However, the electromagnetic emission induced by an input current has remained beyond the realm of molecular simulations. This is the challenge addressed here with the help of an equation of motion for the density matrix coupled to a photon bath based on a Redfield formulation. This equation is evolved within the framework of the driven-Liouville von Neumann approach, which incorporates open boundaries by introducing an applied bias and a circulating current. The dissipated electromagnetic power can be computed in this context from the time derivative of the energy. This scheme is applied in combination with a self-consistent tight-binding Hamiltonian to investigate the effects of bias and molecular size on the electroluminescence of metallic and semiconducting chains. For the latter, a complex interplay between bias and molecular length is observed: there is an optimal number of atoms that maximizes the emitted power at high voltages but not at low ones. This unanticipated behavior can be understood in terms of the band bending produced along the semiconducting chain, a phenomenon that is captured by the self-consistency of the method. A simple analytical model is proposed that explains the main features revealed by the simulations. The methodology, applied here at a self-consistent tight-binding level but extendable to more sophisticated Hamiltonians such as density functional tight binding and time dependent density functional theory, promises to be helpful for quantifying the power and quantum efficiency of nanoscale electroluminescent devices.