I NQR and spectroscopic investigation of impurity-doped and mixed lithium iodate Li1−xHxIO3 crystals

The ¹²⁷I NQR, IR absorption and Raman spectra of impurity-doped and mixed lithium iodate Li_1−xH_xIO₃ crystals grown from water solutions with different LiIO₃/HIO₃ ratios were investigated depending on the content of the impurity hydrogen x. The NQR results suggested that, at small concentration of doping iodic acid x<0.22, the lattice dynamics of the crystal grown from water solution changes significantly though the crystal retains hexagonal symmetry. Spectroscopic studies are compatible with average hexagonal symmetry of the grown doped crystals. From the results of Raman studies at room temperature and 100 K, the concentration range of hydrogen dopant 0.22<x<0.36 was found where disordered solid solution crystals Li_1−xH_xIO₃ are formed.     

14N遥测核四极共振中的偏离共振效应

本文对遥测NQR谱中的偏离共振效应作了较详细地研究,发现¹⁴N谱线的强度随偏离共振效应而变化。当偏离共振强度与射频场强度接近时,测得的谱线强度最大。该效应可用来增强¹⁴N遥测NQR谱仪的灵敏度。上述实验现象在理论上采用脉冲的激发带宽方法作了解释和讨论。     

Ab initio calculation of 4-ClC6H4CH2Cl and peculiarities of electron density distribution in this molecule

Ab initio calculation of the 4-ClC₆H₄CH₂Cl molecule was performed by the restricted Hartree-Fock method in the split valence 6–31 G* basis set with complete optimization of its geometry. Populations of p-orbitals of atoms of this molecule were analyzed.³⁵Cl NQR frequencies and asymmetry parameters of the electric field gradient on³⁵Cl nuclei were estimated on the basis of the populations of valent p-orbitals of CI atoms and their components. Good conformity with the experimental values was obtained when only less diffuse components of p-orbitals were used in calculations of populations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 823–826, April, 1996.     

Electronic and Spatial Structure of Piperidine and Its Substituted Derivatives from the Results of ab initio Calculations

The results of non empirical quantum-chemical calculations using the RHF/6-31G(d) and MP2/6-31G(d) methods do not agree with proposals for the axial position of the H atom on the N atom in the piperidine molecule. According to RHF/6-31G(d) calculations for the N-methylpiperidine molecule and its chloro-substituted derivatives an equatorially placed methyl group is energetically more favored than an axial. The axial C-Cl and C-H bonds in these molecules are longer than the equatorial. The ³⁵ Cl NQR frequencies for the axial Cl atoms are lower than the equatorial. The ³⁵ Cl NQR frequency of the axial chlorine atom in 2-chloro-1-methylpiperidine is anomalously low. This is chiefly due to the high population density of its p σ-orbital and this is a result of the polarization of the C-Cl bond via the N atom unshared electron pair directly through the field. The effect of a similar unshared electron pair on the parameters of the C-Cl bond in the ClCH₂NH₂ molecule has been studied by the RHF/6-31(g) method for different angles of rotation of the ClCH₂ group around the C-N bond. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1044–1052, July, 2005.     

On the estimation of the field constant of 35Cl nuclear quadrupole resonance frequency in the series of [R1R2R3AsCl]+M? compounds

The field constant of the NQR frequency of a chlorine atom (³⁵Cl) in a series of arsenic derivatives [R¹R²R³AsCl]⁺M⁻ was estimated from correlations. The field frequency is ∼41.5±3.5 Hz cm kV⁻¹, which is nearly twice as much as that in analogous phosphorus compounds. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1758–1760, August, 2005.     

Ab initio calculations ofp-Cl2C6H4 molecule and its35Cl NQR parameters

Ab initio calculations ofp-dichlorobenzene molecule were carried out using the Hartree-Fock method in the 6–31 G* valence-split basis set. The molecule was also calculated by the MNDO method in the valence sp-basis set for comparison. The populations of the valent p-orbitals of the C and CI atoms were analyzed. The optimized geometry of the molecule as well as its³⁵Cl NQR frequency and the asymmetry parameter of the electric field gradient at the³⁵CI nuclei calculated using the populations of the less diffuse components of the valent p-orbitals of the Cl atoms are in agreement with the corresponding experimental values for the -modification of 1,4-Cl₂C₆H₄.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2177–2179, September, 1996.     

Nuclear quadrupole resonance in 2,4-dinitrochlorobenzene

A study of the spin lattice relaxation (T₁) and the nuclear quadrupole resonance frequency (ν_Q) gives an important information about the dynamics of molecular groups in molecular solids. In the present paper, we analyze the contributions of the reorientational motion of nitro groups of 2,4-dinitrochlorobenzene to the NQR parameters of the chlorine nucleus in the molecule.

We found two contributions to T₁ and ν_Q due to the onset of the reorientation of nitro groups in the molecule; one of these contributions is mostly due to intermolecular effects in the crystal. For the chlorine nuclei, the efficiency of the modulation mechanism is usually provided by the change of the electric field gradient due to the moving molecular group; this gives us a way of how to assign each contribution to T₁ from the ortho and para positions of the NO₂ groups in the molecule. It is observed that there are two different potential barriers depending on the position of the nitro groups in the molecule. The behavior in the temperature dependence of the line width shows a thermal history dependence of the molecular crystal.     

Order-disorder effects of small guests in clathrates studied by nuclear quadrupole resonance and crystallography. Part I. Carbon tetrachloride and related molecules in Ni(SCN)2(3-methylpyridine)4

NQR spectroscopy and X-ray crystallography have been jointly applied to the study of the small guest molecules CH₂Cl₂, CHCl₃, CCl₄, CBr₂Cl₂, C(CH₃)2Cl₂ etc. in the Werner host complex Ni(SCN)₂(3-methylpyridine)₄. Specific host-guest dipole-dipole interactions play an important role in order-disorder effects for guest molecules in the cavities of orthorhombic system,Fddd. Thus a weakly polar molecule such as CBr₂Cl₂ exhibits a disordered alternation, both the bromine and the chlorine atoms occupying the two possible sites in theC ₂ cavity, whereas for the polar molecule C(CH₃)₂Cl₂, an ordered structure is observed. In addition, two new types of crystal structures,C2/c andP , are reported here for dichloromethane and chloroform clathrates.     

Study of isomorphism in fluorine-containing antimony(III) complexes

The mutual influence of the atoms on the composition of solid fluorine-containing antimony(iii) complexes formed in aqueous solutions in the (MF) _x −(M′F) _n−x −SbF₃ (M, M′=Na, K, Rb, Cs, and NH₄;n=1, 2;x=0 to 2), (KNO₂) _n −(KY) _n −SbF₃ (Y=F, Cl, SO₄;n=0.5, 1), and K₂SbF₅−K₂SbCl₅ systems was investigated by elemental, X-ray, and thermogravimetric analyses and by IR and^121,123Sb NQR spectroscopy. The isomorphism conditions for fluorine-containing antimony(iii) compounds resulting in the formation of complexes NaM′SbF₅·1.5H₂O (M′=K and Rb), K₂SbF₅·1.5H₂O, NaCs₃Sb₄F₁₆·H₂O, KsbF₃Cl, K₂SbF₂Cl₃ with constant compositions, continuous M _x M′_2−x SbF₅ (0<x<2) and limited M _x M′_1−x SbF₄ (0.25<x<0.75; M, M′=K, Rb, Cs, and NH₄) solid solutions or LiF+MSbF₄ (M=Na, K, Rb, and Cs), M₂SbF₅+Cs₂SbF₅ (M=Na and K) and MSbF₄+NaSbF₄ (M=Rb and NH₄) mechanical mixtures were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 103–108, January, 1999.     

121,123Sb and 75As NMR and NQR investigation of the tetrahedrite (Cu12Sb4S13) – Tennantite (Cu12As4S13) system and other metal arsenides

This work is motivated by the recent developments in online minerals analysis in the mining and minerals processing industry via nuclear quadrupole resonance (NQR). Here we describe a nuclear magnetic resonance (NMR) and NQR study of the minerals tennantite (Cu₁₂As₄S₁₃) and tetrahedrite (Cu₁₂ Sb₄S₁₃). In the first part NQR lines associated with ⁷⁵As in tennantite and ^121,123Sb isotopes in tetrahedrite are reported. The spectroscopy has been restricted to an ambient temperature studies in accord with typical industrial conditions. The second part of this contribution reports nuclear quadrupole-perturbed NMR findings on further, only partially characterised, metal arsenides. The findings enhance the detection capabilities of NQR based analysers for online measurement applications and may aid to control arsenic and antimony concentrations in metal processing stages.