Magnetic field effects on electron transfer reactions involving sextet-spin (S = 5/2) intermediates generated on photoexcitation of a Cr(III)-porphyrin complex

The excited trip-sextet (⁶T₁) state of chloro-(3-methylimidazol)-(meso-tetraphenylporphyrinato) chromium(III) (Cr^IIIP) is quenched by 1,1′-dibenzyl-4,4′-bipyridinium (BV²⁺) in acetonitrile through electron transfer to give ⁵(Cr^IIIP^·+) and ²BV^·+. The intermediate is a geminate ion pair in the sextet (Sx) state ⁶[⁵(Cr^IIIP^·+) ²BV^·+], which decays through either the escape from a solvent cage to give the free ions or the spin conversion to the quartet (Qa) state followed by back electron transfer. The free ion yield (Φ_FI) increased with increasing magnetic field from 0 to 4 T and then slightly decreased from 4 T to 10 T. These magnetic field effects are explained as follows. Under low fields where the Zeeman splitting of the spin sublevels is lower than or comparable with the electron spin dipole—dipole interaction within ⁵(Cr^IIIP^·+), this interaction effectively induces the Sx → Qa conversion of [⁵(Cr^IIIP^·+)²BV⁺] to result in low Φ_FI values. Under high fields where the Zeeman splitting is larger than the dipole—dipole interaction, the Sx → Qa conversion is decreased with increasing field to cause higher Φ_FI values. The slight decrease in Φ_FI above 4 T may be due to the Δg mechanism.     

Photostimulated electron transfer and its action on paramagnetism of Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The effect of irradiation by ultraviolet light on the effective magnetic moment of a paramagnetic single crystal based on photochrome spiropyran (Sp) and chromium oxalates Sp₃Cr(C₂O₄)₃ molecules is detected. It is shown that the deviation of the temperature dependence of the magnetic moment from the Curie law is caused not by the exchange interaction, but by electron redistribution between Cr³⁺ and Cr⁴⁺ ions and spiropyran molecules Sp⁰ and Sp⁺. Analysis of the angular dependence of EPR spectra makes it possible to determine the contribution of Cr³⁺ ions to the magnetic properties of the crystals and to determine the crystal field parameters D = 0.619 cm⁻¹ and E = 0.024 cm⁻¹. Irradiation of hydrated samples by ultraviolet light leads to intensity redistribution of EPR lines attributed to Cr³⁺ and Sp⁰. Thermally stimulated paramagnetism of triplet states of spiropyran ions Sp⁺ and the SpI salt is observed.     

Anharmonic force constants of GaSb from the measured third order elastic constants at 300°K

The third-order elastic constants of single crystal GaSb are determined using ultrasonic pulse interferometer at 10 MHz. The constants at 300°K, in units of 10¹¹ N.m.⁻², are C_l11 = ™ 4 ·75 ± 0·06 C₁₄₄ = + 0·50 ± 0·25 C₁₁₃ = ™ 3 ·08 ± 0·02 C₁₆₆ = ™ 2·16 ± 0·13 C₁₂₃ = ™ 0 ·44 ± 0·29 C₄₅₆ = ™ 0·25 ± 0·15 These constants are used to evaluate the three anharmonic first and second neighbour force constants based on modified Keating’s model. The constants are (in units of 10¹¹ N.m⁻²)γ=− 2·406;δ=0·407;ε=−0·222.     

Magnetic and transport properties of CuCr1−x VxS2 compounds

A comparison of experimental and calculated effective magnetic moments shows that the sulfur in CuCr_1−x V_xS₂ compounds has two different oxidation states, S¹⁻ and S²⁻, while the vanadium has a higher degree of oxidation (V³⁺) than the chromium (Cr²⁺). A model is proposed to explain the reduction in the activation energy for defect formation in the Cu-sublattice and the rise in the Cu⁺-cation conductivity when chromium is replaced by vanadium. Fiz. Tverd. Tela (St. Petersburg) 41, 1450–1451 (August 1999)     

Progress in pion-decay channelling: Refractory bcc metals at high and low temperatures

By means of π⁺/μ⁺ channelling, positive pions (π⁺) implanted intoTa, Mo, andW are investigated up to high temperatures. A striking observation is that the channelling effect disappears in a rather narrow temperature interval centred at 0.26 (Ta) to 0.51 (W) of the melting temperature. From studies of π⁺ trapping by oxygen atoms inTa estimates for the low-temperature π⁺ diffusivity inTa [D _π(23K)=1.4·10^−10±0.3 m²s⁻¹,D _π(47K)=5.7·10^−10±0.3 m²s⁻¹] as well as for the binding enthalpy of π⁺ to 0 atoms (H _B=7·10⁻² eV) have been obtained. The diffusion data are in reasonable agreement with the theory of phonon-assisted tunnelling.     

Four quasi-particle level at 2256 keV in182Re

In-beam nuclear spectroscopic studies of¹⁸²Re, following the reaction¹⁸¹Ta(α, 3n)¹⁸²Re have been made using gamma-ray and internal conversion electron techniques.K-conversion coefficients for several transitions have been measured and the multi-polarities of the various transitions assigned. In particular, the spin and parity of the four-quasi-particle isomeric level at 2256 keV were determined to be 16⁻. Theg-factor of this level has been measured to beg = 0·32 ± 0·05. On the basis of theg-factor and the decay pattern of this level, a configuration {v9/2⁺ [624↑]v7/2⁻ [514↓]v7/2⁻ [503↑]π9/2⁻ [514↑]} _k ^x = 16⁻ has been assigned to this level. The nature of the retardation of the gamma transitions deexciting this level is discussed. It is argued that the measured retardation factors can be explained if the nucleus has a triaxial shape.     

T-band phenomena in 183Re

Abstact: High-spin states in ¹⁸³Re have been studied using the ¹⁷⁶Yb(¹¹B,4n) reaction at 52 and 57 MeV. Two high-K bands have been observed directly by a time-correlated γ-γ coincidence measurement. One of the bands is built on an isomeric K ^π=(25/2)⁺ state at E _x= 1908 keV with a half-life of 0.82(2) ms. The other band, assigned as K ^π=(29/2)⁻ at E _x= 2739 keV, decays to the (25/2)⁺ band. These bands are interpreted as three-quasiparticle structures, π(5/2)⁺[402] &⊗ν(9/2)⁺[624] ⊗ν(11/2)⁺[615] for the (25/2)⁺ band and π(9/2)⁻[514] ⊗ν(9/2)⁺[624] ⊗ν(11/2)⁺[615] for the (29/2)⁻ band. The K ^π= (29/2)⁻ band becomes strongly Coriolis mixed with increasing spin and is gradually changing into a low-K s-band structure. Received: 20 April 1998     

Comparative Raman study of the Ti complex Cp2Ti(η2-C60) · C6H5CH3 and TixC60 films

Raman spectra from the first Ti fullerene complex Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ are presented. Compared to spectra of pure C₆₀, the spectra of the Ti complex exhibit a number of new peaks due to the symmetry lowering for C₆₀. The A _g(2) mode is downshifted by 12 cm⁻¹ compared to C₆₀, which corresponds to a charge transfer of one electron per Ti-C₆₀ bond. This value (6 cm⁻¹ for one transferred electron) is identical to the downshift of the A _g(2) mode in alkali metal fullerides with ionic bonding. The spectra of Cp ₂Ti(η²-C₆₀) · C₆H₅CH₃ were compared to the spectra of evaporated Ti_xC₆₀ films. The A _g(2) mode in Ti₄C₆₀ showed a downshift of about 25 cm⁻¹ compared to pure C₆₀, which corresponds to a charge transfer of one electron per Ti atom; this is similar to the ionic alkali metal fullerides and different from η²-C₆₀-type bonding. From Fizika Tverdogo Tela, Vol. 44, No. 3, 2002, pp. 483–485. Original English Text Copyright ? 2002 by Talyzin, Jansson, Usatov, Burlakov, Shur, Novikov. This article was submitted by the authors in English.     

Thermal expansion of thin C60 films

The thermal expansion coefficient a and structure of C₆₀ films with thickness t∼3–10 nm were investigated in the temperature interval from room to liquid-nitrogen temperature by electron-optical methods. The thermal expansion coefficient was determined from the temperature shift of the diffraction maxima in the electron diffraction patterns. The objects of investigation were epitaxial C₆₀ films condensed in vacuum on a (100) NaCl cleavage surface and oriented in the (111) plane. A surface-induced size effect in the thermal expansion coefficient was observed. It was established that as t decreases α _f increases and is described well by the relation α _f=17·10⁻⁶ K⁻¹+8.3·10⁻⁵ nm K⁻¹ t ⁻¹. This relation was used to estimate the linear expansion coefficient α _s of the C₆₀ surface in the (111) plane as α _s=60·10⁻⁶K⁻¹, which is several times larger than the bulk value. The experimental results agree satisfactorily with the theoretical calculations of the mean-square displacements of molecules located in a region near the surface. Zh. éksp. Teor. Fiz. 114, 1868–1875 (November 1998)     

Synthesis, Characterization, DNA-Binding and Antiproliferative Activity of Nd(III) Complexes With N-(Nitrogen Heterocyclic) Norcantharidin Acylamide Acid

Three novel complexes [Nd(L)(NO₃)(H₂O)₂]·NO₃·2H₂O (HL¹ = N-pyrimidine norcantharidin acylamide acid, C₁₂H₁₃N₃O₄; HL² = N-pyridine norcantharidin acylamide acid, C₁₃H₁₄N₂O₄; HL³ = N-phenyl norcantharidin acylamide acid, C₁₄H₁₅NO₄) were synthesized. HL¹, HL² and HL³ are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant K_sq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC₅₀ = 131.7 ± 23.4 μmol·L⁻¹) and A549 (IC₅₀ = 128.4 ± 19.9 μmol·L⁻¹) cell lines. The inhibition rates of complex(2) (IC₅₀ = 86.3 ± 11.3 μmol·L⁻¹) are much higher than that of NCTD (IC₅₀ = 115.5 ± 9.5 μmol·L⁻¹) and HL² (111.0 ± 5.7 μmol·L⁻¹) against SMMC7721 cell lines.     

The vibrational spectra and structural properties of Me7Eu2UO2(PO4)5 crystals

We investigate the vibrational spectra of crystals of ternary orthophosphates Me₇Eu₂UO₂·(PO₄)₅ (Me–Na, Rb, Cs) obtained by solid-phase synthesis. We show that in these materials the effect of coordination distorts the geometry of the PO ₄ ³⁻ tetrahedron and decreases its symmetry. We conclude that the PO ₄ ³⁻ tetrahedrons in Me₇Eu₂UO₂(PO₄)₅ occupy two nonequivalent positions in the lattice. The character of manifestation and the number of oscillation frequencies observed allow the assumption that they have the C_3v- and C₂-symmetry. This symmetry of two crystallographically nonequivalent groups of PO ₄ ³⁻ ensures a complete set of bands in the IR absorption spectra of the crystals investigated. We show that these crystals exhibit chain structural motifs. Translated from Zhurnal Prikladnoi Spektroskopii, Vol, 64, No. 4, pp. 467–470, July–August, 1997.     

Determination of Trace Mercury by Solid Substrate-Room Temperature Phosphorimetry Quenching Method Based on Catalytic Effect of Hg2+on Formation of the Ion Association Complex [Sn(XO)6]4+·[(Fin)4]

A new method for the determination of trace mercury by solid substrate-room temperature phosphorimetry (SS-RTP) quenching method has been established. In glycine-HCl buffer solution, xylenol orange (XO) can react with Sn⁴⁺ to form the complex [Sn(XO)₆]⁴⁺. [Sn(XO)₆]⁴⁺ can interact with Fin⁻ (fluorescein anion) to form the ion associate [Sn(XO)₆]⁴⁺·[(Fin)₄]⁻, which can emit strong and stable room temperature phosphorescence (RTP) on polyamide membrane (PAM). Hg²⁺ can catalyze H₂O₂ oxidizing the ion association complex [Sn(XO)₆]⁴⁺·[(Fin)₄]⁻, which causes the RTP to quench. The ΔIp value is directly proportional to the concentration of Hg²⁺ in the range of 0.016–1.6 fg spot⁻¹ (corresponding concentration: 0.040–4.0 pg ml⁻¹, 0.40 μl spot⁻¹), and the regression equation of working cure is ΔIp=10.03+83.15 m Hg²⁺ (fg spot⁻¹), (r=0.9987, n=6) and the detection limit (LD) is 3.6 ag spot⁻¹(corresponding concentration: 9.0×10^–15 g ml⁻¹, the sample volume: 0.4 μl). This simple, rapid, accurate method is of high selectivity and good repeatability, and it has been successfully applied to the determination of trace mercury in real samples. The reaction mechanism for catalyzing H₂O₂ oxidizing the ion association complex ([Sn(XO)₆]⁴⁺·[(Fin)₄]⁻) SS-RTP quenching method to determine trace mercury is also discussed.     

Conservation laws for classical and relativistic collisions. II

On the basis of elementary symmetry arguments it is shown that (1) if in classical mechanics there exists a quantity λ+Σ_iμ_iυ_i+1/2νυ ² that is conserved, where λ,μ _i, andν are particle parameters, then theμ _i andν are all proportional to a single parameterμ and the quantityAμ+Σ_iB_iμυ_i+C(λ+ 1/2Dμυ ²), whereD ≡ν/μ, is conserved for all values ofA, B _i, andC; (2) if in relativistic mechanics there exists a quantity λ+Σ_iμ_iυ_i[1−(υ ²/c ²)]^−1/2+νc[1−(υ ²/c ²)]^−1/2 that is conserved, then theμ _i andν are all proportional to a single parameterμ and the quantityAλ+Σ_iB_iμν_i[1−(υ ²/c ²)]^−1/2+Cμc [1−(υ ²/c ²)]^−1/2 is conserved for all values ofA, B _i, andC.     

The Studies of Enhanced Fluorescence in the Two Novel Ternary Rare-Earth Complex Systems

Two novel ternary rare-earth complexes SmL₅·L^’·(ClO₄)₂·7H₂O and EuL₅·L^’·(ClO₄)₂·6H₂O (the first ligand L = C₆H₅COCH₂SOCH₂COC₆H₅, the second ligand L^’ = C₆H₄OHCOO⁻) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL₅·L^’·(ClO₄)₂·nH₂O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL₅·(ClO₄)₃·2H₂O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Cycloaddition of 2′-azidoethyl glycosides to fullerene[C60] under ultrasonic irradiation

The reactions of fullerene[C₆₀] with 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-α-d-mannopyranoside (2a) and 2′-azidoethyl 2,3,4,6-tetra-O-acetyl-β-d-galactopyranoside (2b) under ultrasonic irradiation cause the cycloaddition of 2′-azidoethyl glycosides to fullerene[C₆₀] and lead to d-glycosyl fullerene[C₆₀] derivatives 3a and 3b, respectively. The glycosyl fullerene[C₆₀] derivatives were characterized by ¹H and ¹³C NMR, UV–vis, FAB-MS, FT-IR spectra and were a 1:1 glycoside fullerene [C₆₀]-adduct.     

Effect of alkali-metal doping on photoluminescence of CdS films

It is established that doping of CdS polycrystalline films with alkaline metals (Li, Na, K, Cs) results in an increase of luminescence intensity by 3–5 times compared with pure films. This increase is accounted for by the placement of alkaline-metal ions in V _Cd ²⁻ cation vacancies, which are nonradiative recombination centers in these films. From the dependences of the luminsecence intensity of the doped films on the synthesis conditions (deposition temperature, concentration of doping impurities, type of doping metal), the parameters that ensure the maximum luminescence intensity of the films are determined as T_dep ≈ 450°C and C_Me = 1·10⁻⁵ at %. The luminescence intensity decreases by 1–3% upon exposure of the films to UV light (λ_max = 365 nm, I = 10²¹ quanta·sec·cm⁻¹) for several hours. This is indicative of the stability of these films against UV radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 362–366, May–June, 2007.     

High-spin isomers in 183Os

High-spin states in ¹⁸³Os have been studied by means of in-beam γ-ray spectroscopy. Two isomers with I ^π= ((43/2)⁻) and (43/2)⁺ have been identified at excitation energies of E _x = 5.068 and 5.168 MeV. The half-lives are determined as T _1/2= 27 ± 3 and 24 ± 2 ns. Received: 22 December 1997     

The infrared and laser Raman spectra of K2Zn(SO4)2 · 6H2O

The Raman spectra of the single crystal of K₂Zn(SO₄)₂·6H₂O belonging toC _2h ⁵ space group in the 40–1200 cm⁻¹ region in different scattering geometries and their spectra ofthe microcrystalline salt in the 1500-50 cm⁻¹ region have been reported. The dynamics of the crystal has been described in terms of 186 phonon modes under the unit cell approximation. The weak bands in the region 400–900 cm⁻¹ have been assigned to the libratory modes of H₂O molecules in contradiction to the assignments reported by Ananthanarayanan. The ambiguities existing in the literature about the assignments ofν ₂ ^c andν ₅ ^c modes of [Zn(H₂O)₆]²⁺ have also been removed. The translatory and libratory modes of different units of the crystal have been identified and assignments are made using farir and Raman data on various isomorphous tutton salts. It has been inferred that both SO ₄ ²⁻ tetrahedron and [Zn(H₂O)₆]²⁺ octahedron undergo linear as well as angular distortions from their free state symmetries in the crystal.     

Muon capture by16O—using a microscopic theory of particle-hole states

The partial capture rates for the process,μ ⁻ +¹⁶O (g·s) →¹⁶N (2⁻, 1⁻, 0⁻, 3⁻) +v _μ have been calculated using the particle-hole wavefunctions obtained using self-consistent procedure. In deriving these wavefunctions, the effectiveN-N interaction has been constructed from the bare Hamada-Johnston interaction. The terms in the muon capture Hamiltonian that depend on the momentum of the capturing proton have been included and their importance in 0⁺ → 0⁻ transition is exhibited. The agreement with the available experimental data is good. The need to incorporate meson exchange effects in 0⁺ → 0⁻ transition is pointed out.