X-ray determination of the mean-square vibrational amplitudes of atoms in nearly perfect CdS crystals

The mean-square amplitudes of Cd and S atoms in CdS were determined for vibrations parallel as well as perpendicular to the c-axis. The results were obtained by measuring the temperature dependence of X-ray integrated intensities for reflections from both basal and prismatic planes in nearly perfect crystals. The analysis of the experimental data is given in detail. The following results were found for T = 295°K: 〈u²_Cd〉_∥ = 2.85±0.04×10^?18cm², 〈u²_s〉_∥ = 1.94 ± 0.08 × 10^?18cm², 〈u²_Cd〉_⊥= 2.39 ± 0.04 × 10^?18cm² and 〈u²_s〉⊥ = 1.63 ± 0.08 × 10^?18cm². The fact that Cd atoms have a larger vibrational amplitude than the S atoms is briefly discussed.     

Magnetic orientation of carbon nanotubes at temperatures of 231 K and 314 K

Carbon nanotubes were placed in magnetic fields of  80.0 kOe at temperatures of 231 K and 314 K. Scanning electron microscopy showed that nanotubes were oriented with the tube axis parallel to the fields. It was also observed that the probability of the orientation became higher, when the temperature was raised from 231 K to 314 K. The anisotropy in the susceptibilities parallel X∥ and perpendicular X _⊥ to the tube axis is suggested to increase with rise in temperature: X∥ ? X⊥ = (4 ± 2) × 10^?6 emu mol^?1 (per mol of carbon atoms) at 231 K and X∥ ? X⊥ = (45 ± 27) × 10^?6 emu mol^?1 at 314 K.     

Supertransferred hyperfine structure in EPR of V4+ ion in Ca3In2Ge3O12 garnet

Interaction of an unpaired electron of the tetrahedral V⁴⁺ ion in Ca₃In₂Ge₃O₁₂ garnet with the four nearest In nuclei gives rise to clearly resolved structure of EPR spectra. We report the observation and analysis of these spectra at three frequencies and at temperature 77 K. The temperature dependence between liquid helium and the room temperatures was also studied. Parameters of the spin Hamiltonian are g_∥=1·8735; g_⊥=1·9825; ∣ ¦A∥|=150·4×10^?4cm^?1; ¦ A_⊥¦ = 36·7 × 10^?4 cm^?1. The supertransferred hyperfine interaction was found to be isotropic, absolute value of the corresponding parameter a is 22·1 × 10^?4 cm^?1.     

Electron paramagnetic resonance of Dy3+ in cubic ZnSe and Tm3+ in hexagonal CdS single crystals

Electron paramagnetic resonance has been observed for Dy³⁺ in ZnSe and Tm³⁺ in CdS. For Dy³⁺ doped ZnSe, an isotropic spectrum was observed having well resolved hyperfine lines due to ¹⁶¹Dy and ¹⁶³Dy. The g value obtained was 6.577 ± 0.002 and ¹⁶¹A was 191 ± 1 × 10⁴ cm^?1 and ¹⁶³A was 265 ± 3 × 10^?4 cm^?1. The agreement of the observed g value to g(τ₆) = 6.667 and the point-charge calculations suggest that Dy³⁺ occupies an interstitial (II) site with no local charge compensation. For Tm³⁺ doped in hexagonal CdS, an axial spectrum consistent with g_⊥ = 0, g_∥ = 10.722 ± 0.007, D = 2.57 GHz (crystal field splitting) and ¹⁶⁹A = 1207 ± 5 × 10^?4cm^?1. The large g_∥ value indicates that the Tm ion exits in the trivalent state. This is in reasonable agreement with previous reports of the non-Kramer's state of Tm³⁺.     

Gleichzeitige Messung von Hyperfeinstruktur,Starkeffekt und Zeemaneffekt des85Rb19F mit einer Molekülstrahl-Resonanzapparatur

A molecular beam resonance apparatus with electric quadrupole lenses asA- andB-fields and with superimposed parallel electric and magnetic transition-fields was used. Molecules in different rotational statesJ, m _J are separated by theA-field. Spectra of molecules in different vibrational states are resolved by their different Starkeffect energies. By this means the following electric and magnetic properties of the molecule could be measured in the rotational stateJ=1 and vibrational statesv=0 and 1: The magnetic and electric dipole moment of the molecule, the scalar and the tensor nuclear dipole — dipole interactiond _s andd _T, the nuclear spinrotational interactionc _F andc _Rb, the nuclear quadrupole interactioneqQ, the nuclear magnetic moment μ_Rb, the anisotropy of the diamagnetic susceptibility ξ_⊥?ξ_∥, the anisotropy of the diamagnetic shielding of the external field by the electrons at the position of the nuclei σ_⊥?σ_∥. Using these quantities it was possible to calculate the quadrupole moment and a weighted quadrupole moment of the electronic charge distribution. The results are: (J=1,v=0) μ_el=8,5464 (17) debμ _J/J=?29,79(2)x10^?6 μ _B d _s/h=0,36(23) kHzd _T/h=0,69(22)kHzc _F/h=10,42(70) kHzc _Rb/h=0,479 (48) kHz.eqQ _Rb/h=?70,3410(26) MHzμ(1?σ_S)Rb=1,3474(5) μ_k (ξ⊥-ξ _∥)=12(6)×10^?30 erg/Gauß² (σ_⊥-σ∥)_Rb=?3,8(2,1)×10^?4 (σ⊥-σ _∥)_F=?2,6(3)×10^?4     

Effect of the spin-orbit interaction of Ni2+ ions with a triplet orbital ground state on the magnetostriction of NiFe0.5Cr1.5O4 ferrite

The magnetization σ and the longitudinal (λ_∥) and transverse (λ_⊥) magnetostrictions of the NiFe_0.5Cr_1.5O₄ ferrite containing the tetrahedral ions Ni²⁺ with the triplet orbital ground state have been investigated for the first time at a temperature of 4.2 K in fields up to 55 kOe. It is revealed that the NiFe_0.5Cr_1.5O₄ ferrite exhibits an anomalously large magnetic anisotropy (H _c=12.5 kOe) and magnetostrictions (λ_∥≈?870×10^?6 and λ_⊥≈800×10^?6). In strong fields, the magnetostrictions λ_∥ and λ_⊥ are found to be anisotropic in character; i.e., the susceptibility Δλ_∥p and Δλ_⊥p. The conclusion is drawn that the studied compound is characterized by two paraprocesses: one paraprocess in the B sublattice has an exchange nature, and the second process in the A sublattice is due to the spin-orbit interaction of Ni _A ²⁺ ions.     

Stress-induced optical dichroism of V−-centers in MgO

The stress-induced optical dichroism and optical absorption spectra of the V^?-centers in electron irradiated MgO are reported. The dichroism spectrum can be largely attributed to a paraelastic alignment of inherently-dichroic V^?-centers. A curve-fit analysis of the lower-energy portions of the dichroism and absorption spectra yields the ratio of the transition dipole strengths, $\text{D}{}_{\mathrm{\parallel }}\text{D}{}_{\mathrm{\perp }}\text{= 1.55 ± 0.2}$, and the energy splitting, E_∥ ? E_⊥ = 0.22 ± 0.07 eV, for light polarized parallel (∥) and perpendicular (⊥) to the defect symmetry axis. The spectra also have considerable intensity in their high-energy tails, and it is speculated that a portion of this intensity is due to the V-center. The implications of the results with regard to the electronic structure of the center are discussed.     

Desorption kinetics and directional dependence of the surface diffusion of potassium on stepped W(100) surfaces

Using a surface ionisation ion microscope the desorption parameters and the diffusion constant of potassium were measured on stepped W(100) surfaces. The activation energy of ionic desorption as well as the corresponding prefactor do not depend on the step density; the mean adsorption lifetime τ can be expressed as τ=1.6×10^?14s exp(2.44 eV/kT).Whereas the surface diffusion of potassium on “flat” W(100) and on W(S)-[9(100)×(110)] was found to be isotropic, on W(S)- [5(100)×(110)] and W(S)-[3(100)×(110)] it occurs preferentially parallel to the step direction. The diffusion constant D_∥ for this direction has roughly the same value for all investigated surfaces: D_∥=7.8×10^?2 cm²s^?1 exp(?0.42 eV/kT). For the direction perpendicular to the steps D⊥ depends on the step density, whereby the activation energy as well as the prefactor increase with increasing step density.     

Electrical and magnetic properties of single crystal [NEt4]2[CuII(mnt)2]

We report electrical and magnetic studies of [NEt₄]₂[Cu^II(mnt)₂]. This crystal is composed of chains of theplanar [Cu^II(mnt)₂]^?2 anions (space group $\text{P}\text{1}$ and z = 1) which exhibit only weak magnetic interactions. The material behaves as a semiconductor; from 300–400°K the conductivity increases by six orders of magnitude and the resistivity values above 300°K are comparable to those of some of the better known wide band-gap inorganic semiconductors. In contrast with the behavior of other linear chain systems, at room temperature the conductivity along the chain (σ_∥) is less than that perpendicular to the chain (σ_⊥). As the temperature is increase, the anisotropy ratio, σ_∥/σ_⊥, becomes greater than unity and increases to 1.6 × 10² at 400°K.     

Tetravalent vanadium in CaF2 and SrF2 crystals: An EPR study

An EPR study of tetravalent vanadium centers created by room temperature X-irradiation in CaF₂ and SrF₂ is presented. The production efficiency of these centers is enhanced by previous annealing of the samples at 1000 K in air. The symmetry of V⁴⁺ ions is tetragonal and its EPR spectrum can be described by an axial spin Hamiltonian including a Zeeman and hyperfine term with $\text{S =}\text{1}\text{2}$ and $\text{I =}\text{7}\text{2}$ (corresponding to ⁵¹V nuclei). The following values for the spin Hamiltonian parameters are obtained g_∥ = 1.947 ± 0.002, g_⊥ = 1.935 ± 0.005, A_∥ = 500 ± 5 MHz, A_⊥ = 150 ± 10 MHz in the case of SrF₂ and g_∥ = 1.945 ± 0.002, A_∥ = 505 ± 5 MHz and A_⊥ < 200 MHz, in the case of CaF₂. A model for the center including an interstitial O^2? ion is tentatively proposed.     

Electron paramagnetic resonance of Dy3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Dy³⁺ ions in lead thiogallate PbGa₂S₄ single crystals have been presented. It has been shown that the ground state of these ions corresponds to the lowest Stark sublevel Γ₆ of the term ⁶ H _15/2. The spectra are well described by the axially symmetric spin Hamiltonian with the effective spin S = 1/2 with the factors g _‖ = 15.06 and g _⊥ = 2.47. The Dy³⁺ ions substitute Pb²⁺ ions in the crystal lattice of PbGa₂S₄. The observed hyperfine structure has allowed to unambiguously interpret the EPR spectra. The hyperfine interaction constants of two odd isotopes of dysprosium in lead thiogallate single crystals have been found to be A _‖ = 675 × 10^?4 cm^?1 and A _⊥ = 111 × 10^?4 cm^?1 for ¹⁶³Dy and A _‖ = 472 × 10^?4 cm^?1 and A _⊥ = 77 × 10^?4 cm^?1 for ¹⁶¹Dy.     

Vibration-rotation spectra of ethane and deuteroethanes: The ν2 band of CH3CD3

The ν₂ band of CH₃CD₃ has been measured under an effective resolution of 0.04 cm^?1. About 400 transitions observed in the region from 2130 to 2060 cm^?1 have been identified as due to the ν₂ fundamental band. The least-squares analysis of these transitions yields the band constants: ν₀ = 2089.957, B′ = 0.548937, D_J′ = 6.97 × 10^?7, D_JK′ = 1.92 × 10^?6, A′ - A″ = ?0.01158, and D_K′ - D_K″ = 1.30 × 10^?6 cm^?1. The ground-state constants B″, D_J″, and D_JK″ are fixed to the values obtained from microwave spectroscopy.     

Analysis of the ν6(A″2) band of cyclopropane-d6 recorded under high resolution

The parallel band ν₆(A″₂) of C₃D₆ near 2336 cm^?1 has been studied with high resolution (Δν = 0.020 – 0.024 cm^?1) in the infrared. The band has been analyzed using standard techniques and the following parameters have been determined: B″ = 0.461388(20) cm^?1, D″_J = 3.83(17) × 10^?7 cm^?1, ν₀ = 2336.764(2) cm^?1, α^B = (B″ ? B′) = 8.823(12) × 10^?4 cm^?1, β^J = (D″_J ? D′_J) = 0, and α^C = (C″ ? C′) = 4.5(5) × 10^?4 cm^?1.     

The analysis of symmetric rotor Raman spectra: The pure rotational spectrum of 11BF3

The pure rotational Raman spectrum of ¹¹BF₃ has been photographed. Great care was taken in the analysis to consider all the unresolved components under each observed Raman line profile. If this is ignored, systematic errors result. The final set of molecular constants obtained was B₀ = 0.34502(±3 × 10^?5)cm^?1, D_J = 4.38(±0.10) × 10^?7cm^?1, and D_JK = ?9.1(±1.0) × 10^?7cm^?1.     

Transport and magnetic properties of multiwall carbon nanotubes before and after bromination

Bulk samples of oriented carbon nanotubes were prepared by electric arc evaporation of graphite in a helium environment. The temperature dependence of the conductivity σ(T), as well as the temperature and field dependences of the magnetic susceptibility χ(T, B) and magnetoresistance ρ(B, T), was measured for both the pristine and brominated samples. The pristine samples exhibit an anisotropy in the conductivity σ_∥(T)/σ_⊥>50, which disappears in the brominated samples. The χ(T, B) data were used to estimate the carrier concentration n ₀ in the samples: n _0ini ～3×10¹⁰ cm^?2 for the pristine sample, and n _0Br～10¹¹ cm^\t—2 for the brominated sample. Estimation of the total carrier concentration n=n _e+n _p from the data on ρ(B, T) yields n _ini=4×10¹⁷ cm^?3 (or 1.3×10¹⁰ cm^?2) and n _Br=2×10¹⁸ cm^?3 (or 6.7×10¹⁰ cm^?2). These estimates are in good agreement with one another and indicate an approximately fourfold increase in carrier concentration in samples after bromination.     

Tunable laser study of the ν10 + ν11 band of cyclopropane

Diode laser measurements of the ν₁₀ + ν₁₁ (l_tot = ±2) perpendicular band of cyclopropane have led to the assignments of roughly 600 lines in the 1880–1920-cm^?1 region. Most of the spectra were recorded and stored in digital form using a rapid-scan mode of operating the laser. These spectra were calibrated, with the aid of a computer, by reference to the R lines of the ν₁ + ν₂ band of N₂O. The ground state constants we obtained are (in cm^?1) B = 0.670240 ± 2.4 × 10^?5, D_J = (1.090 ± 0.054) × 10^?6, D_JK = (?1.29 ± 0.19) × 10^?6, D_K = (0.2 ± 1.1) × 10^?6. The excited state levels are perturbed at large J values, presumably by Coriolis couplings between the active E′(l_tot = ±2) and the inactive A′(l_tot = 0) states. Effective values for the excited state constants were obtained by considering only the J < 15 levels. The A₁-A₂ splittings in the K′ = 1 excited states were observed to vary as q_effJ(J + 1), with q_eff = (2.17 ± 0.17) × 10^?4 cm^?1.     

Far-infrared rotational spectra of some freons; chlorotrifluoromethane,dichlorodifluoromethane, and trichlorofluoromethane

The far-infrared rotational spectra of chlorotrifluoromethane, dichlorodifluoromethane, and trichlorofluoromethane have been observed with an interferometric (Fourier transform) spectrometer in the region 10–40 cm^?1 at a resolution of 0.07 cm^?1. CCl₂F₂ exhibits a continuum spectrum at this resolution, but symmetric top rotational fine structure is observed for CClF₃ and CCl₃F. Isotope splitting is also observed in CClF₃, and analysis yields the rotational constants for C³⁵ClF₃ of B₀ = 0.11112 cm^?1, D_J = 1.6 × 10^?8cm^?1; and for C³⁷ClF₃, B₀ = 0.10835 cm^?1, D_J = 1.5 · 10^?8cm^?1. Isotopic shifts can be allowed for in CCl₃F to yield constants for C³⁵Cl₃F of B₀ = 0.0821 cm^?1, D_J = 1 × 10^?8cm^?1. These values are all in agreement with those deduced from microwave studies of the low J transitions apart from B₀ for C³⁵ClF₃, where the difference is outside the expected experimental error.     

Ethane spectrum between 1940 and 2152 cm−1: Ground state parameters

The absorption spectrum of ethane was recorded between 1940 and 2152 cm^?1 at a resolution of 0.025 cm^?1. Ground state parameters were determined from the principal band in this region, ν₉ + ν₁₂(E_u): B₀ = 0.6630353 cm^?1, D₀^J = 1.0406 × 10^?6 cm^?1, D₀^JK = 2.575 × 10^?6 cm^?1 (standard errors are 7, 8, and 13, respectively, in the last digits quoted). The quoted values are from the analyses of 269 ground state combination differences, the standard deviation of the least-squares analysis was 0.0032 cm^?1.     

Infrared rotation-vibration spectra of ethane: The perpendicular band, ν7, of C2H6

The study of the gas-phase infrared spectrum of C₂H₆ in the region of the perpendicular CH-stretching band, ν₇, near 3000 cm^?1 is extended for the ΔK = + 1 subbands as far as K = 20. The spectral resolution of ～0.030 cm^?1 is increased to ～0.015 cm^?1 by deconvolution. The earlier investigation of this band for KΔK = +9 to ?5, is repeated with greater accuracy, providing more reliable ground-state constants (cm^?1): B₀ = 0.663089 ± 24, D₀^J = (0.108 ± 4) × 10^?5, D₀^JK = (0.50 ± 7) × 10^?5. The molecular constants (cm^?1) for the ν₇ fundamental are B₇ = 0.66310 ± 3, A₇ = 2.682, ν₀ = 2985.39, ζ₇ = 0.128. A discussion of resonance effects in this band, in particular x-y-Coriolis and Fermi resonance, is given.     

A high-resolution study of the 14.4-μm infrared band of deuterofluoroform

The FT-IR spectrum of the ν₃ parallel band of deuterofluoroform has been recorded at a resolution of 0.0045 cm^?1. Nine independent spectral parameters were determined which reproduce some 650 observed wavenumbers with a standard error of 3 × 10^?4 cm^?1. The constants derived for the ν₃ band are (in cm^?1): ν₀ = 694.2822(3); B₀ = 0.3309321(9); B₃ = 0.3302464(11); α^B = 6.859(10) × 10^?4; α^C = 1.429 × 10^?4; D₃^J = 3.168(3) × 10^?7; D₀^J = 3.188(3) × 10^?7; D_JK³ = 4.766 × 10^?7; D_JK⁰ = 4.864 × 10^?7; and D_K⁰ ? D_K³ = 2 × 10^?10.