Y2O3·Cr2O3复合氧化物热力学性质的研究

在1182—1386K温度范围内,用固体电解质氧浓差电池:Mo|Cr,Y₂O₃,Y₂O₃·Cr₂O₃|ZrO₂(+MgO)|Cr,Cr₂O₃|Mo测定了复合氧化物Y₂O₃·Cr₂O₃的热力学性质。对于反应Y_{2关键词：}     

Magnetic circular dichroism of the first spin-forbidden transition in 2[Cr(en)3Cl3] . KCl . 6H2O

The longitudinal Zeeman effect of the ² E ←⁴ A ₂ transition of the Cr⁺³ ion in single crystals of 2[Cr(en)₃Cl₃] . KCl . 6H₂O has been measured using circularly polarized light as a function of magnetic field strength between 0 and 160 kgauss at ～80 K. The g factor for the ground state was determined to be g _‖(⁴ A ₂) = 2·01±0·05, in agreement with the E.S.R.-determined value. The ratio between the excited state g values and that of the ground state was determined; using the value g _‖(⁴ A ₂) = 1·99, the g factors g _‖(2) = 2·61±0·04 and g _‖() = 1·47±0·04 were obtained.     

Magnetic properties of the compounds N(CH3)4MnIIMIII(CN)6 ·8 H2O(MIII = Mn,Fe)

In the isostructural cyanobridged chain compounds N(CH₃)₄Mn^IIM^III(CN)₆ · 8H₂O high spin Mn(II) ions couple antiferromagnetically to low spin Mn(III) of Fe(III) ions. The Mn^II–Mn^III compound orders ferrimagnetically below T_N = 28.5 ± 1 K. The tetragonal a and b axes are easy ones for the magnetic moments. In the Mn^II–Fe^III compound antiferromagnetic order occurs below T_N = 9.3 K, with spins aligned along the tetragonal c axis. The compound undergoes a meta-magnetic transition from the antiferromagnetic to a ferrimagnetic phase. This occurs at 2 K for a field H_crit ≈ 1.2 T. The temperature dependence of H_crit, which vanishes at T_N, is followed. The tricritical temperature T¹ is ～ 5 K.     

Hadron structure in the ladder model (II)

The (flavor non-singlet) probability Φ(k) to find a far-off-shell quark in a hadron is obtained in the renormalization group improved ladder model for QCD in the space-like axial gauge in the region k_T²??2k·P, extending an earlier result for the region k_T²≈?2k·P. The resulting Drell-Yan cross section at measured Q_T agrees in the appropriate limit with that given by Parisi and Petronzio (and disagrees with the DDT form). By using a soft photon method in an abelian gauge theory, I argue that ladder diagrams with strong ordering of gluon q· P's in fact dominate Φ(k) in the high-energy limit considered.     

Dipole ordering and ionic conductivity in NASICON-Type Na<Subscript>3</Subscript>Cr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> structures

The aspects of structure, dipole ordering, and ionic conductivity of the Na₃Cr₂(PO₄)₃ crystal with the four polymorphic phases (α, α', β, and γ) have been investigated. The features of the α-Na₃Cr₂(PO₄)₃ crystal structure and its dipole ordering and relaxation polarization in the low-temperature α and α' phases have been refined. The occurrence of Na₃Cr₂(PO₄)₃ dipole ordering in the α and α' phases and high ionic conductivity in the β and γ phases is attributed to the structural changes in the rhombohedral [Me₂(PO₄)₃]^–3_3∞ crystal frame upon phase transformations α → α', α' → β, and β → γ. A model for explaining the dipole ordering and ionic conductivity phenomena in Na₃Cr₂(PO₄)₃ is proposed.     

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.     

Crystalline complexes of fullerene with anisole derivatives

For the first time, bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· and a crystalline complex of fullerene with ortho-butoxyanisole have been obtained. The temperature dependence of the parameters of the EPR spectrum of bis(anisole)chromium fulleride (PhOMe)₂Cr^+·[C₆₀]^−· has been studied. The molecular structure of the complex of fullerene with ortho-butoxyanisole has been established.     

Spin relaxation of charged centers in silicon in the presence of photocarriers (Si: Cr+, [Cr+−B−])

Spin relaxation of deep charged centers Cr⁺ and of donor-acceptor pairs (Cr⁺?B^?)⁰ in silicon is studied by nonstationary EPR spectroscopy at liquid-helium temperatures. We observed the effect of an increase in the spin-lattice relaxation rate under band-to-band sample illumination; the magnitude of the effect is proportional to the photoelectron concentration. The spin-dependent carrier trapping is shown to play a dominant role in spin relaxation under illumination for centers of both types. Coupled rate equations describing the interaction of various subsystems with one another and with the bath are solved. A comparison of experimental data with theory yielded the electron trapping cross sections σ_r(Cr⁺)?4.9×10^?12 cm² and σ_r(Cr⁺?B^?)?1.6×10^?12 cm² at T=4.2 K. The results obtained are discussed in terms of the theory of trapping by attractive centers.     

Some detailed investigations of optically detected Ē(2 E) →4 A 2 cross relaxation in ruby

Cross relaxation betweenē(² E) and⁴ A ₂ states of Cr³⁺ in ruby at an applied external magnetic field ofH=5336 Oe was measured by monitoring the ¦? 1/2〉_ex→ ¦? 3/2〉_g optical transition in the temperature region of 1.6 to 4.2 °K. The chromium concentration varied from 2.9· 10^?4 to 4 · 10^?6 Cr³⁺/Al³⁺. With a concentration greater than 2 · 10^?5, the light intensity of the observed transition increases when cross relaxation takes place, while below this value it decreases. By measurement of the fluorescent intensity of one transition and simultaneously inducing EPR ground state transitions, we monitored the effect of trapping. Taking the value for trapping from fluorescence decay time measurements, we have used rate equations for calculating the actual change of excited state population when cross relaxation occurs. With this phenomenological model we are able to explain our experimental data. Finally some calculations for the effective spin temperature in theē(² E) state as a function of Cr³⁺ concentration as well as for various applied magnetic fields have been done.     

27Al Magic Angle Spinning Nuclear Magnetic Resonance Study of Al1−x Cr x K(SO4)2·12H2O (x = 0, 0.07, and 0.2)

The physical properties of Al_1?x Cr _x K(SO₄)₂·12H₂O (x = 0, 0.07, and 0.2) were studied as a function of temperature using magic angle spinning nuclear magnetic resonance for ²⁷Al. On the basis of the physical properties of pure AlK(SO₄)₂·12H₂O, the effects of partially replacing Al³⁺ with Cr³⁺ ions were examined. Molecular motion changed with the concentration of Cr³⁺ ions. The relaxation process near 320 K was found to undergo molecular motion as described by the Bloembergen–Purcell–Pound theory. The activation energies, phase transition temperatures, and spin–lattice relaxation times in the rotating frame T _1ρ changed with the concentration of paramagnetic ions.     

Angular correlation measurement in the B11(d,pγ)B12 reaction

Thep-γ angular correlations in B¹¹(d, p)B¹² reaction have been measured in both reaction and azimuthal planes for proton angles 35° at E_D=1.60 and 2.40 MeV. The correlation coefficient A ₂ ⁰ and the distortion parameterλ were calculated. The obtained values of the shift of the symmetry axis from the recoil direction, Φ₀ and the parameterλ are far from there plane wave limits. The anisotropy of the angular correlation gives two possible values, 1⁺ and 2⁺, for the spin of the first excited state of B¹².     

An investigation of theL 2-L 3 Coster-Kronig transition probability for 63≦Z≦96

Nuclear spin polarization in the 4f ¹⁴6s ^{2 1} S ₀ ground state of¹⁷⁵Lu⁺(I=7/2) ions is achieved by optical pumping with the resonance line (¹ S ₀-¹ P ₁,λ=261.5 nm). Nuclear magnetic resonance of the free ions in He buffer gas yields for the magnetic dipole momentμ(¹⁷⁵Lu)=2.2240(11)μ _n (with diamagnetic correction). This value can be used for a more accurate determination of the magnetic dipole moments of other Lu isotopes from knownA factor ratios. A comparison with nuclear induction measurements in solids results in the chemical shiftsδ(LuB₁₂)=?23(5)·10^?4 andδ(LuSb)= ?31(5)·10^?4.     

Synthesis and characterization of hexakis(acetonitrile)chromium(III) tetrafluoroborate, [Cr(NCMe)6][BF4]3. A nonaqueous Cr source

Oxidation of [Cr^II(NCMe)₄][BF₄]₂ with thianthrinium tetrafluoroborate forms [Cr^III(NCMe)₆][BF₄]₃ exhibiting two ν_CN absorptions at 2331 and 2301 cm⁻¹, and has been structurally characterized with an average Cr-N distance of 1.999 Å. From the electronic absorption spectra the ligand field splitting, Δ₀, is 20,160 cm⁻¹, which is slightly larger than [Cr^III(OH₂)₆]³⁺ in accord with the divalent chromium analogues. The 298 K ESR has a resonance at g=1.9884, and the magnetic susceptibility has a 300 K moment of 3.85μ_B characteristic of S=3/2 Cr(III). The field dependence of the magnetization can be fit to the Brillouin function also characteristic of S=3/2.     

Dielectric and proton relaxation from ammonium ion motion in alum

Dielectric losses and proton spin lattice relaxation T₁ and T_1? give identical correlation times in NH₄Al(SO₄)₂ · 12H₂O from 75 to 200 K. This is explained as hopping of NH⁺₄ between two positions with different orientations and electric dipole moments.     

Chromium dihydride (CrH2): theoretical evidence for a bent 5B2 ground state

Ab initio molecular electronic structure theory has been used to study two likely candidates for the quintet ground state of CrH₂ at the self-consistent field, the single and double excitation configuration interaction (CISD), the single and double excitation coupled cluster (CCSD), and the single, double, and perturbative triple excitation coupled cluster (CCSD(T)) levels of theory. The largest basis sets utilized for geometry optimizations, designated two-f TZ2P, have a contraction scheme of Cr(14s11p6d2f/10s8p3d2f), H(5s2p/3s2p). At the CCSD(T) level of theory using this two-f TZ2P basis, a bent (C_2v symmetry) ⁵B₂ state is predicted to lie a mere 4·2 kcal mol^-1 (4·5 kcal mol^-1 including zero-point vibrational energy correction) lower in energy than linear (D_∞h symmetry) ⁵Σ_g ⁺ HCrH. Theoretical predictions for the equilibrium geometry, harmonic vibrational frequencies, and isotopic frequency shifts of the ⁵B₂ state compare favourably with the results of recent matrix isolation FT-IR work by Xiao, Hauge, and Margrave. The two-f TZ2P CCSD(T) optimized geometry of ⁵B₂ CrH₂ is r _e = 1·658 Å and ?_e = 114·4° (118° ± 5° is the experimentally estimated bond angle), while the harmonic vibrational frequencies are ω₁(a₁) = 1710, ω₂(a₁) = 582, and ω₃(b₂) = 1683 cm^-1 (experimentally assigned fundamentals in an argon matrix are the symmetric stretch 1651 cm^-1 and asymmetric stretch 1615 cm^-1). Isotopic frequency shifts of CrD₂ relative to CrH₂ are Δω₁(a₁) = -492 and Δω₃(b₂) = -477 cm^-1 (compared with symmetric stretch -462 cm^-1 and asymmetric stretch -448-cm^-1 from experiment).     

Optical pumping of ions in buffer gases

Transient signals measured with a pulsed rf-optical pumping method are used to determine longitudinal relaxation rates for Sr⁺ ions (even isotopes) in noble gas buffers. Depolarization cross sections of the electronic spin in the Sr⁺5² S _1/2 ground state for binary collisions with rare gas atoms are deduced. The results for σ(Sr⁺5² S _1/2) in Ų are (at temperatures between 374 and 449 °K): 2·10^?5(He),4·10^?5(Ne), 5.7·10^?3(Ar), 1.8·10^?2(Kr), and 4.0·10^?2(Xe). These cross sections for the Sr⁺ ion are about two to three orders of magnitude larger than the corresponding ones for the isoelectronic neutral Rb atom. The large increase of the Sr⁺ relaxation rates is explained with the relaxation mechanism of spin-orbit coupling, taking into account two “indirect” effects of the ionic charge: the increase in the gas kinetic cross sections and the more intimate collisions of the Sr⁺ ion with the noble gas atoms. The depolarization is shown to be predominantly due to short-range interactions. A contribution to the relaxation of the Sr⁺ ion from Sr⁺-noble gas molecule formation, induced by three-body or resonant two-body collisions, could not be established for applied pressuresp between 1.5 and 15 Torr of Ar, Kr, and Xe.     

The 4 A 2→2 E transitions of 2[Cr(en)3Cl3]KCl. 6H2O in strong magnetic fields

The Zeeman effect of the R absorption lines for the pure compound 2[Cr(en)₃Cl₃]KCl.6H₂O has been measured photographically, using a strong pulsed magnet with fields of up to 200 000 gauss at 77 K. The results indicate g _∥ (⁴ A ₂) = 1·82 , g _⊥(⁴ A ₂) = 1·90 with g _∥(ē) = -1·82 and g _∥ (2ā) = 1·82. The uncertainties are of the order of ± 0·05.     

Investigation of β+β+ and β+/EC decay of 106Cd

A low background scintillation detector with a CdWO₄ crystal of 1.046 kg was used to search for β⁺β⁺ and β⁺/EC processes in ¹⁰⁶Cd. For the neutrinoless mode the limits T_1/2(0νβ⁺β⁺) ≥ 2.2 · 10¹⁹ y and T_1/2(0νβ⁺/EC) ≥ 5.5 · 10¹⁹ y were obtained with 90% C.L. For the possible two neutrino decay limits of T_1/2(2νβ⁺β⁺) ≥ 9.2 · 10¹⁷ y and _1/2(2νβ⁺/EC) ≥ 2.6 · 10¹⁷ y have been determined with 99% C.L.     

Investigation of224Ra in the226Ra(α, α′ 2n) reaction

Positive and negative parity bands have been followed up to 10⁺ (possibly 12⁺) and 11^? in²²⁴Ra and are compared to the corresponding bands in the isotone²²⁶Th. If a constant value of the intrinsic quadrupole moment is assumed for allE2 transitions in²²⁴Ra theE1/E2 branching ratios are consistent with an intrinsic dipole moment of ¦Q₁¦=0.032(3)e·fm. This small value, as compared to ¦Q₁¦=0.30(2)e·fm for²²⁶Th, can be explained by an almost complete cancellation of large positive liquid-drop and negative shell-model contributions.