Density-functional study of small neutral and cationic bismuth clusters Bi(n) and Bi(n) (+)(n=2-24)

Density-functional theory with scalar-relativistic pseudopotential and a generalized gradient correction is used to calculate the neutral and cationic Bi(n) clusters (2< or =n< or =24), with the aim to elucidate their structural evolution, relative stability, and magnetic property. The structures of neutral Bi clusters are found to be similar to that of other group-V elemental clusters, with the extensively studied sizes of n=4 and 8 having a tetrahedron and wedgelike structure, respectively. Generally, larger Bi clusters consist of a combination of several stable units of Bi(4), Bi(6), and Bi(8), and they have a tendency to form an amorphous structure with the increase of cluster sizes. The curves of second order energy difference exhibit strong odd-even alternations for both neutral and cationic Bi clusters, indicating that even-atom (odd-atom) sizes are relatively stable in neutral clusters (cationic clusters). The calculated magnetic moments are 1micro (B) for odd-atom clusters and zero for even-atom clusters. We propose that the difference in magnetism between experiment and theory can be greatly improved by considering the orbital contribution. The calculated fragmentation behavior agrees well with the experiment, and for each cationic cluster the dissociation into Bi(4) or Bi(7) (+) subclusters confirms the special stability of Bi(4) and Bi(7) (+). Moreover, the bond orders and the gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital show that small Bi clusters would prefer semiconductor characters to metallicity.     

CsPb3Bi3Te8 and CsPb4Bi3Te9: low-dimensional compounds and the homologous series CsPbmBi3Te5 + m

Two new thermoelectric materials of quaternary bismuth telluride CsPb3Bi3Te8 and CsPb4Bi3Te9 are reported, which are members of a homologous series featuring anionic slabs [PbmBi3Te5 + m]- (m = 1-4) of monotonically increasing thickness.     

Electrochemical aspects and structure characterization of VA-VIA compound semiconductor Bi2Te3/Sb2Te3 superlattice thin films via electrochemical atomic layer epitaxy

This paper concerns the electrochemical atom-by-atom growth of VA-VIA compound semiconductor thin film superlattice structures using electrochemical atomic layer epitaxy. The combination of the Bi2Te3 and Sb2Te3 programs and Bi2Te3/Sb2Te3 thin film superlattice with 18 periods, where each period involved 21 cycles of Bi2Te3 followed by 21 cycles of Sb2Te3, is reported here. According to the angular distance between the satellite and the Bragg peak, a period of 23 nm for the superlattice was indicated from the X-ray diffraction (XRD) spectrum. An overall composition of Bi 0.25Sb0.16Te0.58, suggesting the 2:3 stoichiometric ratio of total content of Bi and Sb to Te, as expected for the format of the Bi2Te3/Sb2Te3 compound, was further verified by energy dispersive X-ray quantitative analysis. Both field-emission scanning electron microscopy and XRD data indicated the deposit grows by a complex mechanism involving some 3D nucleation and growth in parallel with underpotential deposition. The optical band gap of the deposited superlattice film was determined as 0.15 eV by Fourier transform infrared spectroscopy and depicts an allowed direct type of transition. Raman spectrum observation with annealed and unannealed superlattice sample showed that the LIF mode has presented, suggesting a perfect AB/CB bonding in the superlattice interface.     

Dispersion interactions between neighboring Bi atoms in (BiH3)2 and Te(BiR2)2

Triggered by the observation of a short Bi⋯Bi distance and a Bi Te Bi bond angle of only 86.6° in the crystal structure of bis(diethylbismuthanyl)tellurane quantum chemical computations on interactions between neighboring Bi atoms in Te(BiR₂)₂ molecules (R = H, Me, Et) and in (BiH₃)₂ were undertaken. Bi⋯Bi distances atoms were found to significantly shorten upon inclusion of the d shells of the heavy metal atoms into the electron correlation treatment, and it was confirmed that interaction energies from spin component‐scaled second‐order Møller–Plesset theory (SCS‐MP2) agree well with coupled‐cluster singles and doubles theory including perturbative triples (CCSD(T)). Density functional theory‐based symmetry‐adapted perturbation theory (DFT‐SAPT) was used to study the anisotropy of the interplay of dispersion attraction and steric repulsion between the Bi atoms. Finally, geometries and relative stabilities of syn–syn and syn–anti conformers of Te(BiR₂)₂ (R = H, Me, Et) and interconversion barriers between them were computed. © 2018 Wiley Periodicals, Inc.     

Design in solid state chemistry based on phase homologies. Sb4Te3 and Sb8Te9 as new members of the series (Sb2Te3)m.(Sb2)n

Sb4Te3 and Sb8Te9 are members of the homology (Sb2Te3)m.(Sb2)n, with structures consisting of Sb2- and Sb2Te3-type slabs stacked along [001]; electrical conductivity and thermopower are reported for several members of this family.     

Syntheses and characterization of some mixed Te/Se polychalcogenide anions [Te(m)Se(n)]2-

Several mixed Te/Se polychalcogenide anions [Te(m)Se(n)](2-) were synthesized at 293 K by reactions between Te(n)(2-)and Se(n)(2-) anions in N,N-dimethylformamide (DMF) in the presence of different-size ammonium or phosphonium cations, in some cases in the presence of metal species. The structures of these anions were determined by single-crystal X-ray diffraction methods. The crystal structures of [NEt(4)](2)[Te(3)Se(6)] (1) and [NEt(4)](2)[Te(3)Se(7)] (2) consist, respectively, of one-dimensional infinite 1(infinity)[Te(3)Se(6)(2-)] and 1(infinity)[Te(3)Se(7)(2-)] anionic chains separated by NEt(4)(+) cations. In compound 1, each chain comprises Te(3)Se(5) eight-membered rings bridged by Se atoms. The Te(3)Se(5) ring has an "open book" conformation. The NMR spectrum of a DMF solution of [NEt(4)](2)[Te(3)Se(6)] crystals at 223 K shows (77)Se resonances at delta = 290, 349, and 771 ppm and a single (125)Te resonance at delta = 944.7 ppm. In compound 2, each chain comprises Te(3)Se(6) five- and six-membered rings bridged by Se atoms. The Te(3)Se(6) ring can be regarded as an inorganic analogue of bicyclononane. The anion of [PPh(4)](2)[Te(2)Se(2)] (4) contains a Se-Te-Te-Se chain with the terminal Se atoms trans to one another. The new compounds [PPN](2)[TeSe(10)] (3), [NMe(4)](2)[TeSe(3)].DMF (5), and [NEt(4)](2)[TeSe(3)] (6) contain known anions.     

Structure and bonding in cyclic isomers of B2AlH(n)(m) (n = 3-6, m = -2 to +1): a comparative study with B3H(n)(m), BAl2H(n)(m) and Al3H(n)(m)

The structure, bonding and energetics of B(2)AlH(n)(m) (n = 3-6, m = -2 to +1) are compared with corresponding homocyclic boron, aluminum analogues and BAl(2)H(n)(m) using density functional theory (DFT). Divalent to hexacoordinated boron and aluminum atoms are found in these species. The geometrical and bonding pattern in B(2)AlH(4)(-) is similar to that for B(2)SiH(4). Species with lone pairs on the divalent boron and aluminum atoms are found to be minima on the potential energy surface of B(2)AlH(3)(2-). A dramatic structural diversity is observed in going from B(3)H(n)(m) to B(2)AlH(n)(m), BAl(2)H(n)(m) and Al(3)H(n)(m) and this is attributable to the preference of lower coordination on aluminum, higher coordination on boron and the higher multicenter bonding capability of boron. The most stable structures of B(3)H(6)(+), B(2)AlH(5) and BAl(2)H(4)(-) and the trihydrogen bridged structure of Al(3)H(3)(2-) show an isostructural relationship, indicating the isolobal analogy between trivalent boron and divalent aluminum anion.     

Variable-range hopping conductivity in Lu-doped Bi2Te3

The Seebeck coefficient enhancement due to an increase of density-of-states effective mass of electron has been found in n-type Bi_1.9Lu_0.1Te₃. This enhancement is assumed to be related to forming the narrow and non-parabolic impurity (Lu) band with local maximum of electronic density of states lying near the Fermi level. Minimum in the specific electrical resistivity, ρ, originated from change of conductivity mechanism was observed at temperature T_m ≈ 11 K. Above T_m, the ρ change is due to decrease of electron mobility via acoustic phonon scattering. Below T_m, the variable-range hopping conductivity takes place. The electron hops between the localized states of the impurity energy band occur via tunneling process. Using the temperature and magnetic field dependences of ρ, the localization radius of electron was estimated as ≈6 nm. Two parts in the magnetic field dependence of the electrical resistivity were found at temperature of 2 K. At weak magnetic fields, the ρ change is in agreement with the variable-range hopping conductivity mechanism. At high magnetic fields, the positive and almost linear transverse and longitudinal magnetoresistances were observed at low temperatures. Both variable-range hopping conductivity and positive linear magnetoresistance are characteristics of disordered and inhomogeneous semiconductors.     

Flat-structural Motives in Small Alumino-Carbon Clusters C(n)Al(m) (n = 2-3, m = 2-8)

Small clusters consisting of a carbon diatom or triatom and several aluminum atoms are investigated ab initio, at an MP2 level of theory. The mainly ionic character of C-Al bonding predominantly leads to structures different from corresponding hydrocarbons (also if starting from analogous initial geometries), while still producing closed-shell ground states. It is found that in many cases stable geometries correspond to flat CAl(3) units. These include unique metal-framed dicarbon and tricarbon all-flat species with unusual planar tetra-coordination. Another frequent feature is a hyper-coordination of carbon atoms, supported by their high negative charges and critically examined via atom-in-molecule calculations. Also characterized are anionic states, electronic excitation and ionization, electron attachment and detachment, and charge distributions.     

Te(CN)4] versus [Te(CN)3(micro-CN)](n)

Solvent molecules have a great influence on the structure and stability of tellurium tetracyanide; whereas Te(CN)4 x (diglyme)(2) contains monomeric Te(CN)4 units, [Te(CN)3(micro-CN) x diglyme](n) is a coordination polymer.     

Rb(4)Hg(5)(Te(2))(2)(Te(3))(2)Te(3), [Zn(en)3](4)In(16)(Te2)4(Te3)Te22, and K2Cu2(Te2)(Te3): novel metal polytellurides with unusual metal-tellurium coordination

Three novel metal polytellurides Rb(4)Hg(5)(Te(2))(2)(Te(3))(2)Te(3) (I), [Zn(en)(3)](4)In(16)(Te(2))(4)(Te(3))Te(22) (II), and K(2)Cu(2)(Te(2))(Te(3)) (III) have been prepared by solvothermal reactions in superheated ethylenediamine at 160 degrees C. Their crystal structures have been determined by single-crystal X-ray diffraction techniques. Crystal data for I: space group Pnma, a = 9.803(2) A, b = 9.124(2) A, c = 34.714(7) A, Z = 4. Crystal data for II: space group C2/c, a = 36.814(7) A, b = 16.908(3) A, c = 25.302(5) A, beta = 128.46(3) degrees, Z = 4. Crystal data for III: space group Cmcm, a = 11.386(2) A, b = 7.756(2) A, c = 11.985(2) A, Z = 4. The crystal structure of I consists of 1D infinite ribbons of [Hg(5)(Te(2))(2)(Te(3))(2)Te(3)](4-), which are composed of tetrahedral HgTe(4) and trigonal HgTe(3) units connected through the bridging Te(2-), (Te(2))(2-), and (Te(3))(2-) ligands. II is a layered compound containing InTe(4) tetrahedra that share corners and edges via Te, Te(2), and Te(3) units to form a 2D slab that contains relatively large voids. The [Zn(en)(3)](2+) template cations are filled in these voids and between the slabs. The primary building blocks of III are CuTe(4) tetrahedra that are linked by intralayer (Te(3))(2-) and interlayer (Te(2))(2-) units to form a 3D network with open channels that are occupied by the K(+) cations. All three compounds are rare polytelluride products of solvothermal reactions that contain both Te(2) and Te(3) fragments with unusual metal-tellurium coordination.     

Sulfonato-encapsulated bismuth(III) oxido-clusters from Bi2O3 in water under mild conditions

Treatment of Bi(2)O(3) with the acids; S-(+)-10-camphorsulfonic, 2,4,6-mesitylenesulfonic and sulfamic, under sonication at room temperature in water for 2-4 h, results in the formation and subsequent crystallisation of polynuclear bismuth oxido-clusters; [Bi(18)O(12)(OH)(12)(O(3)S-Cam)(18)(H(2)O)(2)], [Bi(38)O(45)(O(3)S-Mes)(24)(H(2)O)(14)] and [Bi(6)O(4)(OH)(4)(O(3)SNH(2))(6)].     

Activation cross-section and isomeric cross-section ratio for the 122Te(n,2n)121m,gTe process

Journal of Radioanalytical and Nuclear Chemistry - Measurements of the cross-section for the 122Te(n,2n)121mTe and 122Te(n,2n)121gTe reactions and their ratio within the energy range of...     

Synthesis and crystal structure of a mixed-ligand bismuth(III) complex, [Bi2(phen)2Br5(NO3)] n (phen = 1,10-phenanthroline)

Complex [Bi₂(phen)₂Br₅(NO₃)] _n has been synthesized by reaction of Bi(NO₃)₃ with potassium bromide and 1,10-phenanthroline. The complex has been isolated and characterized by IR-, ¹H NMR-, ¹³C NMR spectrum and elemental analysis. The structure of the [Bi₂(phen)₂Br₅(NO₃)] _n was confirmed by X-ray crystallography which shows the complex to be a one-dimensional polymer as a result of bridging bromides. The two Bi atoms have different environments, six and seven coordinate.     

CsMBi(3)Te(6) and CsM(2)Bi(3)Te(7) (M = Pb, Sn): new thermoelectric compounds with low-dimensional structures

The new materials CsPbBi(3)Te(6) and CsPb(2)Bi(3)Te(7) were discovered through reactions of CsBi(4)Te(6) with PbTe, whereas the isostructural materials CsSnBi(3)Te(6) and CsSn(2)Bi(3)Te(7) were discovered through corresponding reactions with SnTe. The compounds can also be prepared from stoichiometric mixtures of Cs(2)Te, Pb (Sn), Bi, and Te. The crystal structures show a layered architecture of NaCl-type slabs alternating with layers of Cs atoms. This group of compounds offers a new quaternary system, Cs-M-Bi-Te (M = Pb and Sn), available for thermoelectric investigations, including fine-tuning of compositions and doping.