Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Magnetic and electrical properties of Mg1−x CuxO solid solutions and magnetic shielding in Cu-Mg1−x CuxO structures

Mg_1−x Cu_xO solid solutions having an NaCl structure with 0⩽x⩽0.20 are synthesized and Cu-Mg_1−x Cu_xO structures are prepared for superconductivity studies. The magnetic susceptibility χ, electron paramagnetic resonance (EPR), and electrical conductivity of the solid solutions are studied at temperatures of 5–550 K. It is shown that χ ⁻¹(T) obeys the Curie-Weiss law with a paramagnetic Curie temperature Θ close to zero and an effective magnetic moment μ _eff=1.9 μ _B, close to the 1.73 μ _B of a Cu²⁺ ion with spin S=1/2. The width ΔH of the EPR line depends weakly on temperature and increases as x is raised. The volume narrowing of the EPR linewidth ΔH is used to estimate the exchange interaction parameter, 3×10⁻⁴ eV. The g-factor is close to 2 and is temperature independent. The electrical conductivity of Mg_1−x Cu_xO at T=300 K is ≈10⁻¹¹–10⁻¹² Ω⁻¹ cm⁻¹ for x=0 and increases to 10⁻⁵–10⁻⁶ Ω⁻¹ cm⁻¹ for x=0.15–0.20. The conductivity is p-type. Magnetic shielding is observed in Cu-Mg_1−x Cu_xO structures with x=0.15 and 0.20. The possible connection of this phenomenon with interference superconductivity in the contact layer of the structure is discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 293–296 (February 1999)     

Crystallographic and magnetic phase transition in TlMnCl3

The results of our NMR, EPR and magnetic susceptibility measurements in the paramagnetic state of TlMnCl₃ are reported here. The NMR paramagnetic shift of thallium is found to be small but positive. Mn²⁺ EPR line is exchange narrowed. The susceptibility measurements indicate an antiferromagnetic transition. The heat of crystallographic phase transition ΔH, in TlMnCl₃ has been measured using differential scanning calorimetry. The crystallographic phase transition appears to be first order and ΔH is unusually low viz. 10 cal mole⁻¹. In the case of KMnF₃ Δ_H, which is reported here for the first time, is determined to be 2 cal mole⁻¹.     

EPR of trivalent iron ions in a LiCaAlF6 crystal

The orientational dependences of the EPR spectra of Fe³⁺-doped LiCaAlF₆ single crystals (space group P31c, Z=2), grown at the Laboratory of Magnetic Radio Spectroscopy at Kazan’ State University, have been investigated in detail. The spectrum is described by a trigonal spin Hamiltonian with the following parameters: B ₂₀=40.072×10⁻⁴ cm⁻¹, B ₄₀=−5.799×10⁻⁴ cm⁻¹, B ₄₃=−4.281×10⁻⁴ cm⁻¹, A _s=24.33±1, A _p=6.13±1, g _∥=g _⊥=2.00217±0.0003. A theoretical calculation of the hyperfine structure parameters shows that they are described quite well when allowance is made for the overlapping of the wave functions of the paramagnetic center and the ligands (F⁻). Fiz. Tverd. Tela (St. Petersburg) 39, 488–490 (March 1997)     

EPR and Optical Study of Cu<Superscript>2+</Superscript> Ions Doped in Sodium Zinc Sulfate Tetrahydrate Single Crystals

Electron paramagnetic resonance (EPR) study of Cu²⁺-doped sodium zinc sulfate tetrahydrate is done at liquid nitrogen temperature. Two magnetically equivalent sites for Cu²⁺ are observed. The spin-Hamiltonian parameters determined by fitting the EPR spectra to the rhombic-symmetry crystalline field are g _x  = 2.2356, g _y  = 2.0267, g _z  = 2.3472, A _x  = 27 × 10⁻⁴ cm⁻¹, A _y  = 54 × 10⁻⁴ cm⁻¹and A _z  = 88 × 10⁻⁴ cm⁻¹. The ground state wave function is also determined. The g-anisotropy is evaluated and compared with the experimental value. With the help of optical study, the nature of bonding in the complex is discussed.     

EPR and optical absorption studies of Cu<Superscript>2+</Superscript> ions in [ZnPd(CN)<Subscript>4</Subscript>(C<Subscript>4</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O<Subscript>2</Subscript>)] single crystals

A Cu²⁺-doped single crystal of catena-trans-bis(N-(2-hydroxyethyl)-ethylenediamine) zinc(II)-tetra-m-cyanopaladate(II) [ZnPd(CN)₄(C₄H₁₂N₂O₂)] complex has been investigated by electron paramagnetic resonance (EPR) technique at room temperature. EPR spectra indicate that Cu²⁺ ions substitute for magnetically equivalent Zn²⁺ ions and form octahedral complexes in [ZnPd(CN)₄(C₄H₁₂N₂O₂)] hosts. The crystal field affecting the Cu²⁺ ion is nearly axial. The optical absorption studies show two bands at 322 nm (30864 cm⁻¹) and 634 nm (15337 cm⁻¹) which confirm the axial symmetry. The spin Hamiltonian parameters and the relevant wave function are determined.     

ESR of V4+ in α-RbTiOPO4 single crystals

We have recorded and investigated the ESR spectrum of vanadium-doped α-RbTiOPO₄ single crystals in the temperature interval 77–300 K. Two types of structurally distinct centers, V1 and V2, with a 4:1 ratio of the peak intensities were observed. The angular dependences of the resonance magnetic fields are described by a spin Hamiltonian corresponding to axial symmetry with the parameters g _∥1=1.9305, g _⊥1=1.9565, A _∥1=−168.2×10⁻⁴cm⁻¹, and A _⊥1=−54.3×10⁻⁴cm⁻¹ for V1 centers and g _∥2=1.9340, g _⊥2=1.9523, A _∥2=−169.0×10⁻⁴cm⁻¹, and A _⊥2=−55.2×10⁻⁴cm⁻¹ for V2 centers. A model of a paramagnetic center is proposed: The vanadium ions replace titanium ions in two structurally distinct positions Ti1 and Ti2 (V1 and V2 centers, respectively). The possibility that a VO²⁺ ion forms when α-RbTiOPO₄ crystals and crystals of the KTP group (KTiOPO₄, NaTiOPO₄, α-and β-LiTiOPO₄), studied earlier, are doped with vanadium is discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 534–536 (March 1998)     

Optical absorption in layered MnGaInS<Subscript>4</Subscript> single crystals

Optical absorption in MnGaInS₄ single crystals has been studied. Direct and indirect optical transitions are found to occur in the range of photon energies of 2.37–2.74 eV and in the temperature range of 83–270 K. The temperature dependence of the band gap has been determined; its temperature coefficients E _gd and E _gi are −5.06 × 10⁻⁴ and −5.35 × 10⁻⁴ eV/K, respectively. MnGaInS4 single crystals exhibit anisotropy in polarized light at the absorption edge; the nature of this anisotropy is explained.     

Quantum oscillations of the resistivity and hall coefficient and the quantum limit in Bi<Subscript>0.93</Subscript>Sb<Subscript>0.07</Subscript> alloys in a magnetic field along the trigonal axis

The dependences of the electrical resistivity ρ and the Hall coefficient R on the magnetic field have been measured for single-crystal samples of the n-Bi_0.93Sb_0.07 semiconductor alloys with electron concentrations in the range 1 × 10¹⁶ cm⁻³ < n < 2 × 10¹⁸ cm⁻³. It has been found that the measured dependences exhibit Shubnikov-de Haas quantum oscillations. The magnetic fields corresponding to the maxima of the quantum oscillations of the electrical resistivity are in good agreement with the calculated values of the magnetic fields in which the Landau quantum level with the number N intersects the Fermi level. The quantum oscillations of the Hall coefficient with small numbers are characterized by a significant spin splitting. In a magnetic field directed along the trigonal axis, the quantum oscillations of the resistivity ρ and the Hall coefficient R are associated with electrons of the three-valley semiconductor and are in phase with the magnetic field. In the case of a magnetic field directed parallel to the binary axis, the quantum oscillations associated both with electrons of the secondary ellipsoids in weaker magnetic fields and with electrons of the main ellipsoid in strong magnetic fields (after the overflow of electrons from the secondary ellipsoids to the main ellipsoid) are also in phase. In magnetic fields of the quantum limit ħω _c /2 ≥ E _F, the electrical conductivity increases with an increase in the magnetic field: σ₂₂(H) ∼ H ^k . A theoretical evaluation of the exponent in this expression for a nonparabolic semiconductor leads to values of k close to the experimental values in the range 4 ≤ k ≤ 4.6, which were obtained for samples of the semiconductor alloys with different electron concentrations. A further increase in the magnetic field results in a decrease of the exponent k and in the transition to the inequality σ₂₂(H) ≤ σ₂₁(H).     

Raman scattering in YBa2Cu3O7 single crystals: Anisotropy in normal and superconductivity states

Precise temperature and polarization dependences of Raman spectra have been investigated for fully oxygenated twin-free YBa₂Cu₃O₇ single crystals. We have found a striking superconductivity-induced x−y anisotropy in the temperature behavior of the 340 cm⁻¹ line: the magnitudes of the softening and broadening are quite different in the xx-and yy-polarizations. This anisotropy suggests a contribution of the CuO-chain superconductivity with a pairing symmetry different from that for the CuO₂ plane, or indicates that the superconducting gap amplitudes are different in the k _x and k _y directions. The d+s gap symmetry is the only realistic symmetry in the case of Δ_x≠Δ_y. Fiz. Tverd. Tela (St. Petersburg) 40, 403–412 (March 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

Hydrogen diffusion constants in stainless steel and Pd60Ag40 alloy, and permeability of diaphragms made of these metals

Hydrogen permeability through diaphragms made of 12X18H12T stainless steel and Pd₆₀Ag₄₀ alloy under electrolytic hydrogen saturation has been studied with an electrolytic cell with a vacuum chamber. Hydrogen diffusion constants D _H = 3.86 × 10⁻¹⁰ cm² s⁻¹ for stainless steel and D _H = 4.36 × 10⁻⁸ cm² s⁻¹ for Pd₆₀Ag₄₀ alloy have been determined at a temperature of 40°C using the Berrer relations.     

Giant negative magnetoresistance in a nonmagnetic semiconductor

Studies of a classical III–V semiconductor (InSb) doped with 3d magnetic ions (Mn²⁺, having a localized spin S=55/2) reveal some unexpected transport properties. It is found that the transition from the metallic to the low-temperature insulator phase occurs at an impurity concentration N _Mn∼N _cr=2× 10¹⁷ cm⁻³ and a temperature T<T _cr∼1 K. Under these conditions a giant negative magnetoresistance arises. The experimental results can be explained in terms of the onset of a hard Mott-Hubbard gap Δ in the impurity band formed by the shallow manganese acceptor in InSb at N _Mn∼N _cr. A model describing the gap formation is proposed. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 5, 358–362 (10 March 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

EPR spectra of the excited nitrogen state in 6H-SiC

A study is reported of donor EPR spectra in compensated 6H-SiC crystals with donor concentrations (N _D -N _A ) varied from 8×10¹⁷ to 5×10¹⁶ cm^?3, performed within a temperature interval from 77 to 170 K at a frequency of 37 GHz. A second paramagnetic state of nitrogen in silicon carbide has been found to exist, and it is associated with its excited 1S(E) state becoming paramagnetic after thermal ionization of the donor electrons from the 1S(A ₁) to 1S(E) level. The EPR spectrum of nitrogen in the 1S(E) state is a single line with an anisotropic width because of the unresolved hyperfine structure. A light-induced charge transfer between the ground, 1S(A ₁), and excited, 1S(E), nitrogen states has been observed. The valley-orbit splitting and the energy required to ionize donor electrons from the 1S(E) to higher lying excited states have been determined for the cubic nitrogen sites. The parameters of a structural defect, characteristic of n-type 6H-SiC compensated crystals, have been established.     

Anisotropy of rotation of nitroxide probes in nematogenic liquid crystals

An electron paramagnetic resonance (EPR) line shape simulation for nitroxide spin probes in the motional narrowing region was carried out assuming axially symmetricg andA tensors and with different anisotropies of rotationN (=R _∥/R _⊥) whereR _∥ andR _⊥ are, respectively, elements of the diffusion tensor along and perpendicular to its principal axisz′. In addition, it was assumed that the principal axes of the diffusion tensor coincide with the molecular axes. Each of three casesz′=x,z′=y andz′=z, which result from cyclic permutations of the molecular axesx, y andz with thez′,y′ andx′ axes of the diffusion tensor, yields its typical EPR spectrum characterized by the relative intensities of the low-, center- and high-field lines. The parameter δ defined by and calculable from the intensities of the three lines was found to vary linearly withN for thez′=x andz′=y cases and, as anticipated, to be practically constant at a value of 1 for thez′=z case. This suggested a method for estimatingN for a probe from its EPR spectrum. Experimental spectra over a narrow temperature range (1°C) in the vicinity of the nematic-to-isotropic transition (about 34.6°C) ofN-(4-n-butylbenzilidene)-4-amino-2,2,6,6-tetramethylpiperidine-1-oxide at a mole fraction of 1·10⁻³ in 4-n-pentyl-4′-cyanobiphenyl showed a pattern of peak heights characteristic of thez′=x case with δ values that gave, neglecting effects of the mean field, higher and lowerN values in the nematic and isotropic regions, respectively. Analysis of other similar systems in the literature gave similar results.     

Determination of temperature in a plasma jet emanating from a plasma torch with sectioned inter-electrode insert from the molecular emission spectrum of nitrogen

Results of application of a method for measuring the distribution of temperature in a nitrogen plasma jet emanating from a dc plasma torch with sectioned inter-electrode insert from the relative intensities of the molecular emission bands of nitrogen in the N₂ ⁺(B²Σ_u ⁺ − X²Σ_g ⁺) first negative and N₂(C³Π_u ⁺ − B³Π_g ⁺) second positive systems are reported. The emission spectra were registered using a small-size spectrometer with medium-range spectral resolution enabling a contour analysis of ro-vibrational bands in molecular emission spectra. The obtained distribution of temperature was compared with the distribution that was determined from the emission lines due to copper atoms and with the mean-mass plasma temperature of the air plasma jet.     

Thermally stimulated luminescence and electron paramagnetic resonance studies of actinide doped calcium chloro phosphate

Electron paramagnetic resonance [EPR] and thermally stimulated luminescence [TSL] studies were conducted on self [α]-irradiated²³⁹Pu doped calcium chloro phosphate andγ-irradiated²³⁹Pu/²³⁸UO ₂ ²⁺ doped calcium chloro phosphate to elucidate the role of the electron/hole traps in thermally stimulated reactions and to obtain trap parameters from both TSL and EPR data. TSL glow peaks around 135 K (# peak 1), 190 K (# peak 2), 435 K (# peak 5) and 490 K (# peak 7) were observed and their spectral characteristics have shown that Pu³⁺ and UO ₆ ⁶⁻ act as luminescent centres in calcium chloro phosphate with respective dopants. EPR studies have shown the formation of the radical ions H⁰, PO ₄ ²⁻ , O⁻, O ₂ ⁻ and [ClO]²⁻ under different conditions. Whereas the [ClO]²⁻ radical being stable up to 700 K, was not found to have any role in TSL processes, the thermal destruction of other centres was found to be primarily responsible for the TSL peaks observed. The trap depth values were determined both by using the TSL data and also the temperature variation of EPR spectra of these centres.     

Direct calculation of transition intensities in LiYF<Subscript>4</Subscript>: Nd<Superscript>3+</Superscript>

Duan’s simple model is extended to analyze the mixing of the 4f ^{N − 1}5d configuration with the 4f ^N states. The explicit static coupling and traditional dynamic coupling are considered, and the parameters are fitted according to the absorption spectrum in LiYF₄: Nd³⁺. The parameter values obtained are as follows: T ₃₂ = −28i × 10⁻⁷, T ₅₂ = −1151i × 10⁻⁷, A ₃₂² = 192i × 10⁻¹² cm, A ₅₂⁴ = i × 10⁻¹² cm, A ₇₂⁶ = 54i × 10⁻¹² cm, and A ₇₆⁶ = −680i × 10⁻¹² cm. Compared to the experimental measurements, the present model yields better results than those obtained from the Judd-Ofelt theory. The text was submitted by the authors in English.     

Addition and spin exchange rate constants by longitudinal field μSR: The Mu+NO reaction

The addition reaction Mu+NO+M→MuNO+M and the spin exchange reaction Mu(↑) +MO(↓)→Mu(↓)+NO(↑) have been measured by longitudinal field μSR at room temperature in the presence of up to 58 atm of N₂ as inert collider. The pressure dependence of the longitudinal relaxation rate due to the addition reaction (λ_c) demostrates that the system is still in the low pressure regime in this pressure range. The corresponding termolecular rate constant has been determined ask _0,Mu =(1.10±0.25)×10⁻³² cm⁶ molecules⁻² s⁻¹, almost 4 times smaller than the corresponding H atom reactionk _0,H=3.90×10⁻³² cm⁶ molecules⁻² s⁻¹ [I.M. Campbell et al., J. Chem. Soc. Faraday Trans. 1.71 (1975) 2097]. The average value of the spin exchange rate constants in the 2.5–58 atm pressure range,k _SE=(3.16±0.06)×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, is in good agreement with previous values obtained by transverse field μSR [D.G. Fleming et al., J. Chem. Phys. 73 (1980) 2751].