An intrinsic property of the hartree-fock model?

The linear relationship between expectation values <rⁿ₁₂ >^{?$\text{1}\text{n}$} and the nuclear charge is shown to be a consequence of the reliability of the screening approximation for atomic properties.     

Study of hyperfine interactions by Mössbauer spectroscopy in mixed crystals

A mixed crystal technique, appropriate for the Mössbauer study of hyperfine interactions in molecules with D > 0, is described. It is based on the magnetic behavior of a |±$\text{1}\text{2}$〉 Kramers doublet. The method has been applied with success to the study of hyperfine structure of Fe(methdtc)₂Br.     

Effect of inorganic aqueous anions on the synergic extraction of cadmium and zinc with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-one (HPMBP) and lipophilic ammonium salts

As a part of a systematic study of the synergic extractions of metals with mixtures of acidic chelating extractants and lipophilic anion-exchangers (B, X with X^?6 inorganic anion), the extractions of M  Cd and Zn from perchlorate, nitrate and sulphate media with 1-phenyl-3-methyl-4-benzoyl-pyrazol-5- one (HL) and tri-n-octylammonium salts (TOAH.X) or aliquat 336 (TOMA.X) in toluene have been investigated. Three key equilibria describe the extractions: (a) M²⁺+2$\text{HL}$?$\text{ML}{}_2$+2H⁺. (b) $\text{B.X}$ +$\text{HL}$?$\text{B.L}$+H⁺+X^? with B efficiency TOMA < TOAH and X efficiency ClO₄ < NO₃ < SO₄. (c) $\text{ML}{}_2$+$\text{B.L}$?$\text{B.ML}{}_3$ with B efficiency toma > TOAH and Ni ～ Co > Cd > ZN.As a consequence of the conflicting orders of efficiencies of TOMA and TOAH in equilibria b and c, TOAH.X is a better synergic extractant from perchlorate medium than TOMA.X whereas the inverse is observed from nitrate and sulphate media. Equilibrium c is independent of the inorganic anions. Constants of equilibria a, b and c are given. B.ML₃ species are not extracted in 1-octanol.     

Etude par diffraction de neutrons de la phase Sr0,5La1,5Li0,5Fe0,5O4

A neutron diffraction study has been carried out on Sr_0.5La_1.5Li_0.5Fe_0.5O₄ of K₂NiF₄-type derived structure and it has shown that iron in the tetravalent state has a high spin configuration (t³_2ge¹_g) and that the material has some stacking defects. At room temperature this compound shows an ordering between iron and lithium atoms leading to a nuclear cell a₀√2, a₀√2, c₀ (a₀ and c₀ are the parameters of the K₂NiF₄-type cell). At low temperature ($\text{T <}\text{T}{}_{\mathrm{<mtext>N</mtext>}}\text{2}$) the magnetic structure can be described as antiferromagnetic, corresponding likely to a colinear pattern with a propagation vector of 0.5 ($\text{2π}\text{a}{}_0$) along the [110] axis. At higher temperature ($\text{T}{}_{\mathrm{<mtext>N</mtext>}}\text{2}\text{< T < T}{}_{\mathrm{<mtext>N</mtext>}}$) helimagnetic structure is consistent with a propagation vector of 0.47 ($\text{2π}\text{a}{}_0$) [110].     

Optical activity of oriented molecules III. The absorption process and the vibrational coupling effects for the tensor of rotation

Equations for the rotation and the ellipticity of samples exhibiting linear and circular birefringence and dichroism (i.e. for small elliptical birefringence and dichroism) are given. By this a second presentation of the frequency dependence for linear and circular birefringence of anisotropic solutions is developed. The absorption coefficients of anisotropic solutions for linearly polarized light are calculated from the H-matrix of Gō. For a special type of orientational distribution function the absorption behaviour is analysed. Within the adiabatic approximation and by neglecting the variation of the electronic transition moments with the nuclear distances, the structure of a circular dichroism band is independent of the orientational distribution function. Empirically, this is not the case for α, β-unsaturated keto steroids. By including this variation in the adiabatic approximation the coordinates of the tensor of rotation R^NnKk_ij are altered by different amounts due to the coupling by vibrations of the involved states with other electronic states of the system (Herzberg-Teller method). As a consequence of this coupling electric dipole and magnetic dipole/electric quadrupole transition moments not belonging to the observed transition |K⁰> ← |N⁰> are added to the zeroth order tensor of rotation R^NK_ij. Le., first order tensor of rotation R^LM/PR_ij = $\text{1}\text{4}$ <μ_k>_LM|ε_kli <C_tj>_PR + ε_klj<C_lj>_PR}, multiplied by a mixing parameter depending on the type of vibration have to be added to R^NK_ij. As a consequence, the structure of the CD band will depend on the orientational distribution function. The model developed is demonstrated for molecules with symmetry D₂.     

Fluorescence polarization anisotropy and kinetics of malachite green measured as a function of solvent viscosity

The fluorescence kinetics and polarization anisotropy of the triphenylmethane dye malachite green were measured as a function of solvent viscosity. The relationshp between the relaxation kinetics and the solvent viscosity was investigated in order to obtain information on the effect of enviromnental changes on the orientational order of dye molecules in solution. It was found that the fluorescence lifetimes follow an η^{$\text{2}\text{3}$} dependence for 1 < η < 60 P, η^{$\text{1}\text{2}$} dependence for 60 P < η < 1000 P and approach a constant for η > 1000 P. The dependence of the fluorescence decay rates on the solvent viscosity was fit to k = 5 × 10¹⁰η^{?$\text{2}\text{3}$} + 5 × 10⁸ s^?1. The fluorescence polarization anisotropy term, R(0), was also measured as a function of solvent viscosity. A marked decrease in R(0) was observed at a viscosity of 1000 P. For η < 1000 P, R(0) was found to be close to the expected value for a random distribution of molecules, 0.4; and for η > 3000 P, R(0) was measured to be ≈0.11. This small value of R(0) may indicate a nonrand The observed change of the polarization anisotropy with increasing viscosity indicates that the dye molecules become ordered at higher viscosities. This may arise through the formation of a long range order due to lack of rotational deexcitation of the malachite green dye molecules at high viscosities.     

Proton NMR studies of lanthanum nickel hydride: Structure and diffusion

The proton magnetic resonance spectrum of lanthanum nickel hydride LaNi_5.3H₆ was measured over the temperature range 118°K < T < 300°K. The second moment of the absorption at 118°K is M₂ = 13.4 ± 0.3 G². Several possible arrangements of the hydrogen atoms are discussed. Narrowing of the line above 140°K is analyzed in terms of proton diffusion and gives an activation enthalpy E = 21 ± 1 kJ mol^?1, NMR correlation time pre-exponential 0.2 ps < τ_c⁰ < 1.6 ps and a self diffusion coefficient at 300°K of 2 × 10^?12 m² s^?1 < D < 2 × 10^?11 m² s^?1.     

Antiprismatic crystal field and paramagnetic susceptibility of U4+ sulfates

On the basis of the simplified model of the U⁴⁺ ion in a distorted axial crystal field, the temperature dependence of the magnetic susceptibilities of three U⁴⁺ sulfates, U(SO₄)₂ · 4H₂O, U₆O₄(OH)₄(SO₄)₆, and U(OH)₂SO₄, within the temperature range 4.2–300°K has been investigated and interpreted. This model proved to be successful, and the only parameters fitted empirically were the values of the crystal field splitting. The antiprismatic coordination (D_4d) of the uranium ion in these compounds was confirmed and its electronic ground states were determined. The system of two singlets $\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| 3 > ±}\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| ? 3 >}$ originating from the doublet 1 ± 3 > is the ground state of the uranium ion in U(SO₄)₂ · 4H₂O. An analogous system of two singlets $\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| 2 > ±}\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| ? 2 >}$ is the ground state in U₆O₄(OH)₄(SO₄)₆. For U(OH)₂SO₄, the doublet | ± 2 > is the ground state above 21°K, whereas below this temperature it becomes split into the two singlets $\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| 2 > ±}\text{1}\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{| ? 2 >}$, probably because of a crystallographic distortion induced by the cooperative Jahn-Teller effect. Deviations from the D_4d symmetry of the uranium ion coordination occurring in these compounds are discussed.     

Infrared high temperature spectra of aluminium chloride and related species

Isothermal cells of nickel with diamon windows were used to study various melts and vapours by infrared emission, transmission and reflectance techniques in the 860 to 300 K range with an evacuable Fourier transform spectrometer.IR vapour spectra of AlX₃ (X = Cl, Br, I) and GaCl₃ in transmission and emission were measured between 700 and 50 cm^?1. A comparable signal/noise ratio between the transmission and emission spectra was obtained above 200 cm^?1, below 200 cm^?1 the transmission spectra had better quality. The dimer and monemer spectra were assigned in terms of $\text{D}$_2h and $\text{D}$_3h symmetry, respectively, and compared with earlier Raman and IR matrix isolation data.Emission spectra of chloroaluminates AlkAlCl₄ (Alk = Li, Na, K, Rb, Cs) were recorded as melts between 1500 and 50 cm^?1. Increasing distortion of the tetrahedral AlCl^?₄ ion in the series Cs<Rb<K<Na<Li was observed. Emission spectra of AlkAl₂Cl₇ (Alk = Li, Na, K, Cs) indicate $\text{D}$_3d symmetry for Al₂Cl^?₇ with a linear Al-Cl-Al bridge as proposed from earlier Raman data. As a demonstration of reflectance technique an IR spectrum of ZnAl₂Cl₈ at ambient temperature is presented.     

1-methyl-(D3)-trishomocubane

The acid catalysed rearrangement of 8-methyl-pentacyclo(5.4.0.0^2,6.0^3,10.0^5,9)undecan-8-endo-o1 ($\text{8}$) to 3-methyl-(D₃)-trishomocuban-4-o1 ($\text{9}$) provided the key step to the synthesis of the title compound ($\text{11}$).     

Diffusion of point defects participating in solid-phase chemical reactions (trap diffusion): Demonstration for the Ti3+ → Ti4+ transition in corundum

A problem of trap diffusion, that is diffusion of point defects in crystals participating in a solid-phase chemical reaction with motionless impurity ions, is solved. Time dependences of the reaction-front displacement, X_f, and its steepness, $\text{(}\text{?C}\text{?X}\text{)}{}_{\mathrm{f}}$ are determined analytically for N₀ ? C₀ and numerically for all relations of N₀ and C₀$\text{x}{}_{\mathrm{f}}{}^2\text{=2}\text{N}{}_0\text{C}{}_0\text{Dt; (}\text{ac}\text{ax}\text{)}{}_{\mathrm{f}}\text{=0.3C}{}_0{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{(}\text{g}\text{D}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2></mtext>}}$where C₀ and N₀ are the initial concentration of impurity and the eqilibrium defect concentration, respectively, D is a diffusion coefficient, and g is a chemical reaction constant. Dependence of X_f vs C₀ and t is confirmed for oxygen annealing of corundum crystals doped with titanium which, reacting with the point defects, changes its valency. The data are obtained for dependence of displacement X_f upon partial oxygen pressure and thermotreatment temperature as well as upon the sign of the constant electric field applied to the sample. From these data we conclude that the reaction of titanium impurity, changing from the three-valent to the tetravalent state at the activation energy of 80 ± 8.5 kcal/mole is due to anisotropic diffusion of charged aluminum vacancy and holes in the valence band. The diffusion coefficient for that process at 1500°C is estimated to be larger than 10^?5 cm²/sec. Using the trap-diffusion features, the concentration of optical centers of the 0.315-μm absorption band in ruby is also estimated.     

Dynamic metal-ligand coupling in the infrared MCD spectra of the cobalt(II) tetrahalides

The axial single-crystal magnetic circular dichroism spectra of Cs₃ZnCl₅/Co²⁺ and Cs₃ZnBr₅/Co²⁺ have been measured over the 4000–7000 cm^?1 region of the ⁴A₂ → ⁴T₁ (F) transition at ambient and liquid-helium temperature. The B/D and C/D terms obtained give transition moment ratios, 〈t₂∥m∥t₂〉/〈e∥m∥t₂〉, in accord with the value required (?3^{$\text{1}\text{2}$}/2^{$\text{1}\text{2}$}) by a dynamic ligand-polarisation model for d-electron transition probabilities in tetrahedral metal complexes.     

Detection of several electronically metastable atomic states by gas phase EPR

Several atomic metastable species including N(²D_{$\text{5}\text{2}$}), N(²D_{$\text{3}\text{2}$}), N(²P_{$\text{3}\text{2}$}), O(¹D₂), Ne(³P₂), Ar(³P₂), Kr(³P₂ and Xe(³P₂) have been detected by gas phase electron paramagnetic resonance (EPR) in a discharge-flow system. Spectra and absolute concentration are presented.     

Magnetic shift of the quadrupolar nucleus 63Cu in polycrystalline Cu2O

Magnetic shift components can be measured for spin $\text{3}\text{2}$ nuclei experiencing a strong symmetric nuclear electric quadrupole interaction by observation of the features of the NMR powder pattern in the quadrupole regime (ν_Q > ν₀). The perpendicular shift component has been previously measured in several materials by detection of the singularity at the low field edge of the pattern. The first measurement of the parallel shift component, obtained by observation of the high field edge, is reported here. For ⁶³Cu in Cu₂O, σ_| = 0.0021 ± 0.0002.     

Self-diffusion of yttrium in monocrystalline yttrium oxide: Y2O3

Yttrium self-diffusion in monocrystalline yttrium oxide (Y₂O₃) is studied by means of the classical radio tracer technique. The few reliable diffusion data obtained in the temperature range 1600–1700°C lead to the following diffusion coefficient

$\text{D=3.5×10}{}^{\mathrm{?9}}\text{exp}\text{?}\text{72}\text{RT}\text{(}\text{kcal/mole}\text{)}\text{m}{}^2\text{sec}{}^{\mathrm{?1}}$

.Experimental errors on the above numerical values are large and give, for the preexponential and energy terms, respectively:

$\text{2.10}{}^{\mathrm{?7}}\text{<D}{}_0\text{<3.10}{}^{\mathrm{?10}}\text{m}{}^2\text{sec}{}^{\mathrm{?}}$

$\text{62<Q<82}\text{kcal/mole}$

.Nevertheless these results seem in good agreement with those deduced from high-temperature and low-stress creep experiments. The theoretical aspect of self-diffusion of yttrium in Y₂O₃ is studied in terms of point defects and lattice disorder due to the equilibrium between the oxide and its environment. This last part is confined to the restricted range of high oxygen partial pressure in which oxygen interstitials are supposed to be majority defects. Intrinsic and extrinsic diffusion behavior are both considered on the basis of a vacancy diffusion mechanism.     

Conformational dependence of pyranoid rings 1,2-cis-fused to dioxolane rings on the configuration of the dioxolane rings in acetylated derivati

X-Ray and ¹H N.M.R. studies on pyranoid rings 1,2-$\text{cis}$-fused to dioxolane rings in acetylated $\text{D}$-gluco- and $\text{D}$--galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the $\text{D}$-gluco but not in the $\text{D}$-galactopyranose series. The crystal structure of 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-(R)--(l-cyano-ethylidene)-α-$\text{D}$-glucopyranose ($\text{1}$) and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{R}$)-(1-cyano-ethylidene)-α-$\text{D}$-galactopyranose ($\text{2}$)have been determined by X-ray analysis. Lattice parameters for $\text{1}$ are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for $\text{2}$ are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened ⁴C₁ and that of the dioxolane ring as distorted E₁. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The ¹H N.M.R. spectra of $\text{1}$ and $\text{2}$ and 3,4,6-tri-$\text{O}$-acetyl-1,2-O-(S)- and (R)-ethylidene-α-$\text{D}$-glucopyranose ($\text{5}$ and $\text{7}$), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ($\text{R}$)-ethylidene-α-$\text{D}$-galactopyranose ($\text{6}$ and $\text{8}$), and 3,4,6-tri-$\text{O}$-acetyl-1,2-$\text{O}$-($\text{S}$)-and ($\text{R}$)-benzylidene-α-$\text{D}$-glucopyranose ($\text{9}$ and $\text{10}$) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the $\text{D}$-gluco series $\text{1}$, $\text{5}$ and $\text{9}$ may be described as flattened ⁴C₁ and that of $\text{7}$ and $\text{10}$ as ²$\text{S}$₅. The major solution conformation of the pyranoid ring in all compounds in the $\text{D}$-galacto series ($\text{2}$,$\text{4}$,$\text{6}$,$\text{8}$) may be described as flattened ⁴$\text{C}$₁.     

On the planarity of tetracyclo [5.5.1.04,13o10,13] tridecahexaene

MINDO/3 calculations indicate that tetracyclo [5.5.1.0^4,130^10,13] tridechexaene ($\text{1a}$) is nonplanar (D₂ symmetry) in its ground state with pronounced bond alternance.