Correlation between magnetic properties and molecular structure of some metallo-mesogens

The behaviour of a large number of paramagnetic metallo-mesogenic molecules with Cu and VO in different mesophases in a magnetic field was investigated by EPR techniques and magnetic susceptibility measurements. The investigation of the angular dependence of the EPR spectra enabled conclusions to be reached concerning the molecular orientation in the external magnetic field. Temperature dependence magnetic susceptibility measurements were carried out in order to obtain information about the overall susceptibility anisotropy. The good agreement between experimental results and calculated data based on the known increment scheme is obvious. It is shown that the direction of orientation of the molecules in a magnetic field is predetermined by the sum of the anisotropy of the phenyl ring and the chelate core in the molecular structure.     

Molecular symmetry and some molecular magnetic properties in external fields

Consideration is given to the characteristics of the tensors needed to described the magnetization of a molecule in external electric and magnetic fields. For a given molecular symmetry there are usually more independent components than those which are immediately obvious.     

Structure and magnetic properties of some boron containing radicals: A molecular orbital study

Equilibrium geometries, hyperfine coupling constants andg-tensors have been calculated for seven boron containing free radicals using the INDO method.Ab initio calculations are reported for BO and BS.     

On magnetic properties of some molybdenum oxides

The temperature dependence of the magnetic susceptibility for the microcrystalline compounds MoO₂, η-Mo₄O₁₁, γ-Mo₄O₁₁, Mo₁₇O₄₇, Mo₈O₂₃, Mo₉O₂₆, and Mo₁₈O₂₆, respectively, has been investigated between 77 and 550 K at various external fields. The susceptibility increases slightly with temperature for all solids. At low temperatures the changes are more pronounced for η-Mo₄O₁₁, γ-Mo₄O₁₁, Mo₁₇O₄₇, and Mo₁₈O₅₂. The deviations from stoichiometry and the related changes in the concentration of charge carrier have a large influence on the values of the susceptibility. Furthermore, some indications of anistotropy were found.     

Electron transport and magnetic properties of some mixed-valent alkalithiocuprates

Electrical transport properties of some two-dimensional isostructural compounds KCu₄S₃, RbCu₄S₃, and CsCu₄S₃ and a one dimensional conductor Na₃Cu₄S₄ have been investigated. Conductivities have been measured on pelletized materials in the temperature range 300 to 150 K. All of them behave as metallic conductors. The room temperature conductivities of these compounds are KCu₄S₃, 1600 Ω^?1 cm^?1; RbCu₄S₃, 1400 Ω^?1 cm^?1; CsCu₄S₃, 1250 Ω^?1 cm^?1; Na₃Cu₄S₄, 700 Ω^?1 cm^?1. The observed trend in conductivities among the isostructural compounds may be rationalized either on the basis of shortest CuCu distances or on the carrier charge concentrations per unit volume. All of these compounds behave as Pauli paramagnetic materials.     

Transferability of some properties of localized molecular orbitals

The transferability of the first and second order electric moments of localized orbitals have been shown. Some moment characteristics have also been investigated. The standard deviation of first order localized moments is less than 2.0%. The standard deviation of second order electric moment components are larger: although they do not exceed 4.0% for bond orbitals, for lone pair ones they vary about 1.5–10.1%.     

Transferability of some properties of localized molecular orbitals

The localized molecular orbitals of some related ten- and eighteen-electron systems have been studied. The transferability of the kinetic, self-interaction, Coulomb and exchange interaction energies on localized orbitals have been shown. The standard deviation of the kinetic and of the interaction energies (including exchange) are less than 2.5% except for lone pair orbitals of the oxygen atoms where the standard deviation is close to 4%.     

Investigations and molecular modeling of some thermophysical properties of polysulfones

Degradation of commercial polysulfones (PSF) was investigated in air and in inert atmosphere (nitrogen) using thermogravimetric (TG) method. It has been found that the degradation of Udel P-1800 PSF is initiated about 400°C, both in air and in nitrogen. The activation energy of degradation of PSF, (E _a), has been calculated by the Kissinger and Ozawa methods. The value ofE _a about 200 kJ·mol^?1 has been found for both air and nitrogen atmosphere. Experimental results concerning thermal properties of PSF (T _g andT _d,1/2) were compared with those obtained by the computer modeling technique, and a good agreement has been found.     

Restriction on approximations of molecular integrals

The results of LCAO-MO-SCF calculations applied to molecules have to be invariant with respect to orthogonal transformations of the basis set of atomic orbitals. However, if the multicenter repulsion integrals needed for such a calculation are approximated, invariancy will in general not be retained. For two methods of approximation the behaviour of the multicenter integrals under such transformations has been investigated, along with the conditions which have to be fulfilled to ensure this invariancy.

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Zusammenfassung Ergebnisse von LCAO-MO-SCF-Rechungen an Molekülen werden nichtinvariant gegen orthogonale Basistransformationen, wenn für die Mehrzentrenintegrale Näherungsausdrücke verwendet werden. Für zwei Näherungsmethoden wird der Einfluß der Transformationen auf die Mehrzentrenintegrale untersucht; Bedingungen für bestimmte Invarianzeigenschaften werden angegeben.

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Résumé Les résultats d'un calcul LCAO-MO-SCF doivent être invariants par rapport aux transformations orthogonales de la base des orbitales atomiques. Cette invariance n'est en général pas respectée si les intégrales de répulsion multicentriques nécessaires pour un tel calcul sont évaluées d'une manière approchée. Le comportement des intégrales multicentriques lors de telles transformations a été étudié par deux méthodes d'approximation; on a envisagé les conditions à remplir pour satisfaire à l'invariance.

     

Electrical and magnetic properties of some organic charge transfer complexes

Two 7,7,8,8-tetracyanoquinodimethane (TCNQ) complexes with cystein and guanine have been investigated. EPR spin signals of these charge transfer complexes were recorded and the electron spin lattice relaxation time (T₁) temperature dependence was investigated. The electron scattering time, calculated from T₁, agreed reasonably well with that from the current carrier effective mass (as determined through the Hall mobility measurements).     

Rheological properties of sulfur-containing hyperbranched polycarbosilanes and related magnetic compositions

Russian Chemical Bulletin - The rheological properties of hyperbranched polycarbosilanes with butyl and decyl terminal groups and their sulfur-containing analogs were compared. The use of various...     

4A磁性分子筛的制备及吸附性能研究

以尖晶石结构的铁酸镍为磁性载体,采用溶胶-凝胶法制备易于固–液分离的4A磁性分子筛。采用傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、振动样品磁强计(VSM)、N2吸附-脱附测试仪等对样品进行了表征。4A磁性分子筛是Ni Fe2O4和4A分子筛的复合颗粒,粒径在1.8-2μm,比表面积在300-500cm2/g,具有超顺磁性。20%-30%的4A磁性分子筛稳定性和磁回收率较好,静态吸附测试表明磁含量影响分子筛对高浓度乙醇中微量水的吸附。Freundlich模型对静态吸附数据的拟合度高。     

Integral approximations for molecular orbital theory

The electron repulsion integrals arising in LCAO-MO theory are approximated by replacement of the product of two orbitals on different centers by linear combinations of one-center products. The approximation differs from those previously proposed in that the coefficients of the various terms are determined by requiring agreement for certain integrals, and in the emphasis of the role of symmetry in selecting the one-center products. For two-center integrals, the new approximation is significantly better than older approximate methods. Reasons are given for expecting this improvement to extend also to multi-center integrals.

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Zusammenfassung Es wird ein Verfahren zur näherungsweisen Berechnung von Elektronenwechselwirkungsintegralen der LCAO-MO-Theorie beschrieben, bei welchem das Produkt zweier Zustandsfunktionen an verschiedenen Zentren durch eine Linearkombination von Produkten am gleichen Zentrum ersetzt wird. Der Unterschied zu ähnlichen Ansätzen liegt in der Justierung der Koeffizienten. Für Zweizentrenintegrale liefert die hier vorgeschlagene Methode bedeutend bessere Ergebnisse als das Mulliken-Verfahren.

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Résumé Les intégrales de répulsion électroniques intervenant dans la théorie LCAO MO sont calculées d'une manière approchée en remplaçant le produit de deux orbitales sur des centres différents par des combinaisons linéaires de produits à un centre. Cette approximation diffère de celles proposées auparavant par la détermination des coefficients des différents termes au moyen de l'ajustement de certaines intégrales et par l'importance du rôle de la symétrie dans le choix des produits monocentriques. Cette nouvelle approximation est bien meilleure que les anciennes en ce qui concerne les intégrales bi-centriques. Nous donnons des raisons d'espérer que cette amélioration s'étendra aux intégrales polycentriques.

     

Optimal gauge in approximate calculations of molecular magnetic properties

A variational procedure is suggested for determining optimal gauge parameters (such as gauge origin etc.) in calculations of molecular magnetic properties with a finite basis set.     

On the investigation of pseudoscalar molecular properties and polynomial approximations according to Ruch and Schönhofer

Analytic chirality functions in one or more ligand parameters representing pseudoscalar molecular properties are shown to decompose as linear combinations in the elementary chirality functions of a suitable module basis. The implications of this decomposition for an approximation ansatz are considered.     

Local exchange-correlation approximations and first-row molecular dissociation energies

Recent Xα calculations of bond energies and other related properties of first-row diatomic molecules show very encouraging agreement with experiment. In the worst cases, however, the Xα dissociation energies overestimate the experimental values by almost 2 eV. Therefore, we have examined several refinements of the Xα theory and their effects on molecular bond lengths, bond energies, and vibrational frequencies. Among them, gradient corrections to the Xα exchange energy and also some variations of the local spin-density correlation energy approximation are considered. We find that a local exchange-correlation functional with gradient corrections gives dissociation energies in significantly better agreement with experiment than the Xα approximation.