Intermolecular hydrogen bonds, rotational spectrum, and structure of van der Waals complexes of (CH3)2O?CF2CH2 and (CH3)2O?CF2CHF

The results of molecular beam Fourier transform microwave (FTMW) investigations of the van der Waals complexes of dimethyl ether with 1,1-difluoroethene/trifluoroethene are reported. The rotational parameters of the complexes have been interpreted in terms of a C_s geometry with the two methyl groups lying out of the σ_v symmetry plane of complexes. The complexes are bound with three hydrogen bonds of which one is the stronger O?HC type and two are the weaker F?HC types. Some additional information on the structure and the hydrogen bond has been obtained from ab initio calculations.     

Microwave substitution structure of the amine group in meta-chloroaniline C6H4CINH2

Microwave spectra of amine-deuterated species of 3-³⁵Cl-aniline, C₆H₄CINH₂, have been observed. The two amino hydrogen atoms are found to be out of the plane of the aromatic ring, and appear to be farther out of the plane when the amine group is deuterated. It has also been shown that the H_trans, c coordinate (0.300 Å) is larger than the cis one (0.281 Å).     

Microwave spectrum of the heterodimers: CH3OH-CO2 and CH3OH-H2CO

Molecular complexes, dimers and heterodimers often show interesting structures, large amplitude internal motions and orientations for reaction coordinates. These properties were the motivations for the current study of the rotational spectra of the heterodimers, CH₃OH-CO₂ and CH₃OH-H₂CO, in a pulsed nozzle Fourier-transform microwave (FTMW) spectrometer. In addition to studying the normal isotopic forms, several isotopologues containing ¹³C or deuterium substituted atoms of each heterodimer were analyzed in order to obtain structural data of the complexes. All species showed splittings from internal rotation of the methyl group and splittings on the b-type transitions of the CH₃OH-H₂CO species suggesting rotation of the H₂CO group between equivalent structural forms. Stark effect measurements on each of the parent species provided dipole moment components. Theoretical ab initio results are compared to the experimentally determined molecular parameters.     

A study on the GVFF of CHF3, CH2F2, and CH3F

The complete GVFF of CHF₃, CH₂F₂, and CH₃F has been calculated from self-consistent-field ab initio energies, using a 4–31 G basis set. The larger part of the interaction force constants is close to those of the best available force fields from experimental data. Only one interaction term in CH₃F and the interaction force constants of the A₁ species in CH₂F₂ differ appreciably from the experimental ones. Using constraints from the ab initio studies we have improved the GVFF of CH₃F and CH₂F₂. It is shown that all comparable stretch-stretch interaction terms are of the same order of magnitude in the three molecules. The sign of all stretch/bend force constants are in accordance with those predicted by the hybrid orbital force field.     

Perturbation of the internal vibrations of (CH3)2S and (CH3)2Se in matrix-isolated complexes with H2O and HCl: Indirect evidence for the trans lone pair effect in (CH3)2X molecules

The formation of hydrogen-bonded complexes (CH₃)₂X ? HA is characterized by small frequency perturbations of the internal vibrations of the base molecules in a low-temperature matrix. Apart from the ν_CXC vibrations the largest shifts are measured in the ν_CH3 spectral region. The unexpected large blue shifts, Δν_CH, are interpreted as an indirect evidence for the existence of the trans lone pair effect in methyl chalcogenides. Additional support is obtained from a comparison between the complexes of HCl and H₂O with (CH₃)₂O, (CH₃)₂S, and CH₃OH.     

Electronic structure and site occupation for the intermediate phase of LaNi4.5Al0.5Hy

The crystal structure, electronic structure and hydrogen site occupancy of LaNi_4.5Al_0.5H_y intermediate phase (y=2.0, 3.0, 4.0) have been investigated using the full-potential linearized augmented plane wave (FLAPW) method. For the first time we analyzed the interstitial site occupation of hydrogen atoms. The H atoms were found to prefer the 6m, 3f and 12n sites, while no 4h sites were occupied. A narrowed Ni-d band is found due to the lattice expansion: the total DOS at E_F increases with y, which indicates that the compounds become less stable. The interaction between Al and Ni, with H plays a dominant role in the stability of LaNi_4.5Al_0.5H_y intermediate phase. The smaller the shift of E_F towards the higher energy region, the more stable the compounds will be. Our results are compared with experimental data and discussed in the light of previous works.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

在H2气氛中Bi2Sr2CaCu2O8+δ的热处理效应

对高品质单相多晶Bi₂Sr₂CaCu₂O_8+δ样品作真空或H₂气氛中不同温度下的热处理。由X射线结构分析,其正常态和超导态性质(特别是载流子浓度)的系统测量结果表明:Bi₂Sr₂CaCu₂0_8+δ样品在H₂气氛中热处理,其氧的释放可分为两个阶段:一是Bi-O层之间的过量氧原子的逸出,降低系统的载流子浓度,从而调节T_c;二是CuO₂面内氧原子的迁移,产生氧空位,使CuO₂面内Cu²⁺的短程二维反铁磁(2D-AFM)有序背景遭到破坏。可以认为:以往文献中报道的Bi₂Sr₂CaCu₂O_8+δ超导体的吸氢效应导致T_c的变化,很可能主要的并不是氢原子的电子掺杂行为,而是与吸氢过程中氧含量的变化相联系。 关键词：     

The ground state rotational spectrum of SO2F2

The analysis of the ground state rotational spectrum of SO₂F₂ [K. Sarka, J. Demaison, L. Margulès, I. Merke, N. Heineking, H. Bürger, H. Ruland, J. Mol. Spectrosc. 200 (2000) 55] has been performed with the Watson’s Hamiltonian up to sextic terms but shows some limits due to the A and S reductions. Since SO₂F₂ is a quasi-spherical top, it can also be regarded as derived from an hypothetical XY₄ molecule. Thus we have developed a new tensorial formalism in the O(3)⊃T_d⊃C_2v group chain (M. Rotger, V. Boudon, M. Loëte, J. Mol. Spectrosc. 216 (2002) 297]. We test it on the ground state of this molecule using the same experimental data (10 GHz-1 THz region, J up to 99). Both fits are comparable even if the formalisms are slightly different. This paper intends to establish a link between the classical approach and the tensorial formalism. In particular, our tensorial parameters at a given order of the development are related to the usual ones. Programs for spectrum simulation and fit using these methods are named C_2vTDS. They are freely available at the URL:http://www.u-bourgogne.fr/LPUB/c2vTDS.html.     

Effect of hydrogen-doping on bonding properties of Ti3SiC2

Using the first principles method based on the density functional theory, we investigated the effect of hydrogen-doping on bonding properties of Ti₃SiC₂. The formation energies of hydrogen interstitials in three possible positions were calculated. The results show that hydrogen favors residing near the (0 0 1) Si plane. In these positions, hydrogen is hybridized most with 1s states of lattice atoms (Si and C), instead of Ti. The presence of hydrogen does not substantially influence the bonding nature of Ti₃SiC₂; chemical bonding is characterized by the hybridizations of Ti d-Si p and Ti d-C p states, and yields high strength. This is contrary to hydrogen-doping in transition metals, where the electron of hydrogen fills in the d bands of the metals and, as a consequence, decreases the cohesive strength of the lattice.