Electrical conductivity of the system Y2O3CeO2

The electrical conductivity of the system Y₂O₃CeO₂ was measured in the temperature range 500–1100°C and P_o2 range 10^–7?10^?1 atm. Possible defect models were suggested on the basis of conductivity data, which were investigated as a function of temperature and of P_o2. The observed activation energies were 0.40 eV and 1.79 eV in the low- and high-temperature regions, respectively. The observed conductivity dependences on P_o2 were in the temperature range 500–750°C and at temperatures from 750–1100°C. It is suggested that the system Y₂O₃CeO₂ shows a mixed ionic plus hole conduction due to an O^″_i defect and an electronic hole conduction due to a V^'''_Y defect in the low- and high-temperature regions, respectively.     

Ni2+ emission in MgO,KMgF3, KZnF3 and MgF2

The emission of Ni²⁺ ions in MgO, KMgF₃, KZnF₃ and MgF₂ crystals has been investigated. The fine structure on the bands at about 20 000 cm^-1 and 13 000 cm^-1 has been studied in detail and from this and the excitation spectra these bands are assigned to ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{A}{}_{\mathrm{2g}}$ and ${}^1\text{T}{}_{\mathrm{2g}}\text{→}{}^3\text{T}{}_{\mathrm{2g}}$ transitions respectively.     

Absorption spectra of Ni2+ in (NH4)2Mg(SO4)2·6H2O and Co2+ in Na2Zn(SO4)2·4H2O

Optical absorption spectra of Ni²⁺ in (NH₄)₂Mg(SO₄)₂·6H₂O and Co²⁺ in Na₂Zn(SO₄)₂·4H₂O single crystals have been studied at room and liquid nitrogen temperatures. From the nature and position of the observed bands, a successful interpretation could be made assuming octahedral symmetry for both the ions in the crystals. The splitting observed for ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band in Ni²⁺ and ${}^4\text{T}{}_{\mathrm{2g}}\text{(F)}$ band in Co²⁺ at liquid nitrogen temperature have been explained as due to spin-orbit interaction. The extra band observed at 16,325 cm^-1 in the case of Ni²⁺ at low temperature has been interpreted to be the superposition of vibrational mode of SO^2-₄ radical on ${}^3\text{T}{}_{\mathrm{1g}}\text{(F)}$ band. The observed band positions in both the crystals have been fitted with four parameters B, C, Dq and ζ.     

Chemiluminescence of IF in the gas phase reaction of I2 with F2

Emission from both the state and the previously unreported $\text{A}{}^3\text{Π}{}_1$ state of IF has been observed in the gas phase reaction of I₂ with F₂ at low pressures. For the state the transition moment and vibrational populations were extracted from the spectra by a least-squares method whereby theoretical band shapes were fit to the experimental data. The effect of flow rates of reactants and Ar on the relative emission from the two electronic states, the effect of pressure on the state, and extinction of emission near 470 nm all favor the population of excited electronic states through a four-center reaction complex, rather than association of F and I atoms.It is argued that there is an avoided curve crossing between the lowest two ³Π_0⁺ states of IF, and that the ground state dissociation energy is 23 229 ± 100 cm^?1. The radiative lifetime of the state is estimated to be 10^?3 sec and to be much shorter than that of the $\text{A}{}^3\text{Π}{}_1$ state.     

Charge density wave commensurability in 2H-TaS2 and AgxTaS2

The charge density wave transition in 2H-TaS₂near 75 K has been observed to be incommensurate, using electron diffraction, with $\text{q}{}^1\text{= (}\text{0.338}\text{±}\text{0.002}\text{)a}{}^1{}_0$ along the 〈10.0〉 directions which, within the experimental uncertainty, remains temperature independent to about 14 K. Incommensurate charge density formation is also observed in Ag_xTaS₂ samples for $\text{x?}\text{0.26}$ with an increase in q¹ to $\text{(}\text{0.347}\text{±}\text{0.002}\text{)a}{}^1{}_0$ when x?0.26. Within the experimental error q¹ appears to be temperature independent to 25 K.     

Opto-electronic properties of CuAlO2

CuAlCO₂ is a p-type semiconductor with an average hole mobility of $\text{1.1 × 10}{}^{\mathrm{?7}}\text{m}{}^2\text{Vs}$. From photoelectrochemical measurements its bandgap is found to be indirect allowed at 1.65 eV; other interband transitions are at 2.3 and 3.5 eV. The valence band is made up mainly from Cu-3d wave functions and lies 5.2 eV below the vacuum level.     

Ultraviolet absorption spectra of Zn2 and Cd2 in solid argon and krypton at 10 K

Zinc and cadmium atoms have been condensed with argon and krypton at 10 K. The most intense absorption is due to the ${}^1\text{P}{}_1\text{←}{}^1\text{S}{}_0$ atomic transition, and a weak band is due to the ${}^3\text{P}{}_1\text{←}{}^1\text{S}{}_0$ atomic absorption. Structured absorptions at 252 and 254 nm in solid argon and krypton with vibrational spacings of 140-120 cm^?1 are due to the ${}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{←}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ transition of Zn₂. Similar 273 and 277 nm absorptions with 110-90 cm^?1 vibrational spacings are due to Cd₂ in solid argon and krypton, respectively.     

Structure,vibrational study and conductivity of the trihydrated uranyl bis(dihydrogenophosphate): UO2(H2PO4)2·3H2O

The X-ray structure (293 K) of UO₂(H₂PO₄)₂·3H₂O has been refined (R = 0.062): M_r = 518g, space group: P2₁/c (Z = 4); $\text{a = 10.816(1)}\text{A}\text{?}$, $\text{b = 13.896(2)}\text{A}\text{?}$, $\text{c = 7.481(1)}\text{A}\text{?}$, β = 105.65(1)^°, $\text{V = 1082.7(2)}\text{A}\text{?}{}^3$; D_c = 3.17 Mg m^?3. The structure consists of infinite chains along the (101) axis with U atoms bridged by two H₂PO₄ groups. The U atom is surrounded by a pentagonal bipyramid of oxygen atoms, one of them being an equatorial water molecule. The cohesion between the chains is ensured by hydrogen bonds involving the two last water molecules. An assignment of IR and Raman bands with isotopic substitution spectra is proposed. A phase transition at 128 K was made evident by DSC and spectroscopy. The room-temperature phase is characterized by a high disorder of the OH bond orientation while in the low-temperature phase H₂O and POH species appear well oriented. The conductivity seems to occur by proton transfer and protonic-species rotation at the POH-water molecular interface between the chains. ac conductivity has been determined by means of the complex-impedance method ($\text{σ}{}_{\mathrm{<mtext>RT</mtext>}}\text{～ (3?12) × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$; E ～ 0.20 eV).     

Electron paramagnetic resonance of 61Ni+ in CuGaS2

EPR of ⁶¹Ni⁺ doped CuGaS₂ at 4.2 K leads to the following experimental data: $\text{g = 1.918 ± 0.006 A  < 12 × 10}{}^{-4}\text{cm}{}^{-1}\text{, g}{}_{\mathrm{\perp }}\text{= 2.328±0.006 A}{}_{\mathrm{\perp }}\text{= (65±2) × 10}{}^{-4}\text{cm}{}^{-1}$. High axial field splitting of ²T₂ state stabilizes the center against Jahn-Teller interaction. Covalency reduction factor k is 0.76.     

The emission spectrum of B2

The emission spectrum of B₂ was reinvestigated under high resolution. Six bands of ¹¹B₂ (0-0, 1-1, 1-0, 2-1, 3-2, and 0–1) as well as four bands of ¹⁰B¹¹B (0-0, 1-0, 2-1, and 3-2) were rotationally analysed. Accurate rotational and vibrational constants were obtained. The triplet character of the transition (${}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{-X}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$) was unambiguously established for the first time and spin-spin interaction constant is obtained for the excited state.     

A study of valency changes of vanadium ions in Al2O3 by γ irradiation

The effect of γ irradiation at 300 K on the concentrations of vanadium ions V³⁺, V⁴⁺ and V²⁺ in Al₂O₃ has been studied quantitatively, using three techniques: optical absorption (V³⁺), low temperature thermal conductivity measurements (V⁴⁺) and EPR (V²⁺). Several single crystals of Al₂O₃ doped with vanadium in a large range of concentration $\text{(2.8 × 10}{}^{18}\text{? 1.3 × 10}{}^{20}\text{at.}\text{cm}{}^3\text{)}$ have been measured. The evolution of the respective concentrations by γ irradiation as a function of the total vanadium content C is quite different in the two regions $\text{C< 1.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ and C larger than this value. A consistent analysis of the results has nevertheless been achieved, leading to the determination of the absolute concentrations of the three ions in the as-received and γ irradiated states for all samples with $\text{C<4.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ (room temperature annealing is observed above this value). The concentrations of V⁴⁺ and V²⁺ ions are always small, but V⁴⁺ ions are more stable: they are present in the as-received state at a level of 1% of the total concentration and a maximum value of $\text{/}\text{?}\text{2.3 × 10}{}^{18}\text{at.}\text{cm}{}^3$ is observed in the γ irradiated state; on the other hand there are less than 4.7 × 10¹⁵V²⁺ ions per cm³ in the as-received state and the maximum value is only $\text{4.2 × 10}{}^{17}\text{at.}\text{cm}{}^3$. Charge transfer between V ions only is not sufficient to explain the experimental results and other defects must be involved in the γ irradiation effect.     

The ground state of methane 12CH4 through the forbidden lines of the ν3 band

High resolution spectra of the ν₃ band of methane, ¹²CH₄, were recorded by using a “third generation vacuum Fourier interferometer”; a large pressure range (from 0.009 to 10 Torr) with a sample path fixed at eight meters was used, enabling observation of transitions with intensity ratios as low as $\text{1}\text{10 000}$. More than 350 forbidden transitions of the ν₃ band, including about 125 transitions of the Q⁺ branch, were unambiguously identified. Of the 277 transitions retained for computations, one-hundred have 11 ≤ J ≤ 16. From combination difference relations using pairs of transitions having the same upper state energy level (forbidden-allowed and forbidden-forbidden pairs were used), 276 independent differences between ground state energy levels could be determined with uncertainties of about 0.001 cm^?1.These data yielded the following values for the ground state structure constants of ¹²CH₄ along with their standard deviations (in cm^?1): $\text{β}{}^{\mathrm{o}}\text{hc}\text{=5.2410356±0.0000096}$, $\text{γ}{}^{\mathrm{o}}\text{hc}\text{=(?1±0.00074) 10}{}^{\mathrm{?4}}$, $\text{π}{}^{\mathrm{o}}\text{hc}\text{=(5.78±0.18) 10}{}^{\mathrm{?9}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.4485±0.0023) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.768±0.126) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.602±0.067) 10}{}^{\mathrm{?11}}$, Thus, for the first time, the scalar constant π⁰ has been evaluated and ir values have been obtained for the two tetrahedral constants ?⁰ and ξ⁰; furthermore, these values are in very good agreement with the ones recently determined from radiofrequency data, i.e., in cm^?1: $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(?1.45061±0.00014) 10}{}^{\mathrm{?6}}$, $\text{?}{}^{\mathrm{o}}\text{hc}\text{=(1.7634±0.0068) 10}{}^{\mathrm{?10}}$, $\text{ξ}{}^{\mathrm{o}}\text{hc}\text{=(?1.5432±0.0040) 10}{}^{\mathrm{?11}}$ From these values, the 276 differences can be reproduced with an overall rms deviation equal to 0.0009 cm^?1.Finally, the ground state energies of ¹²CH₄ have been calculated for J ≤ 16.     

Laser excitation spectra of He2

Metastable $\text{a(2sσ)}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ He₂ molecules are produced by a dc discharge in a flowing He stream. Laser excitation downstream of the discharge produces excitation spectra for a number of He₂ states. LIF spectra are observed for the $\text{(npπ)}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ series for n = 4–9, excepting 5 and the $\text{(npπ)}{}^3\text{Π}{}_{\mathrm{g}}$ series for n = 5–15.     

Electrical transport and magnetic properties of Nd2(WO4)3

Measurements of the molar magnetic susceptibility (X_m) of a powdered sample of Nd₂(WO₄)₃ in the temperature range 300–900 K, and the electrical conductivity (σ) and dielectric constant (?$\text{)}\text{?}$ of pressed pellets of the compound in the temperature range 4.2–1180 K are reported. X_m obeys the Curie-Weiss law with a Curie constant C= 3.13 K/mole, a paramagnetic Curie temperature θ= ?60 K and a moment of Bohr magnetons, p= 3.49 for the Nd³⁺ ion. The electrical conductivity data can be explained in terms of the usual band model and impurity levels. Both the σ and ?$\text{\$}\text{?}$data indicate some sort of phase transition round 1025 K. The conductivity follows Mott's law $\text{σ = A exp (?B/T}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{)}$ in the temperature range $\text{200 < T < 3000}\text{K with}\text{B = 45.00 (}\text{K}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{and}\text{A = 1.38 × 10}{}^{\mathrm{?5}}\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$. The dielectric constant increases slowly up to 600 K, as is usual for ionic solids. The increase becomes much faster above 600 K, which is attributed to space-charge polarization of thermally generated charge carriers.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Spectral and temperature characteristics of Cs2Na(Er,Yb, Y)Cl6 upconverters

Spectral luminescence characteristics of the Cs₂Na(Er, Yb, Y)Cl₆ type upconverter have been measured in the range 300–650 K. A nearly sixfold decrease of the emission intensity of an upconverter was observed in the green area. This emission corresponds to two luminescence transition of Er³⁺ ions: ${}^2\text{H}{}_{\mathrm{<mtext>11</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$ and ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>15</mtext><mtext>2</mtext>}}$. A mechanism of the luminescence intensity decrease has been proposed, in which deexcitation of the ${}^4\text{S}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ level to the ${}^4\text{I}{}_{\mathrm{<mtext>13</mtext><mtext>2</mtext>}}$ level is caused by a neighbouring Er³⁺ ion being excited to the ${}^4\text{I}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ level.     

High-resolution infrared spectrum of the ν2 and ν8 bands of CH2D2

A high-resolution infrared spectrum of methane-d₂ has been measured in the C-D stretching band region (2025–2435 cm^?1). Rotational structures of the ν₂ and ν₈ bands have been assigned by use of the ASSIGN-diagram method, and the c-type Coriolis interaction between ν₂ and ν₈ has been analyzed. The band origins, ν₂ = 2203.22 ± 0.01 cm^?1 and ν₈ = 2234.70 ± 0.01 cm^?1, the rotational constants and the centrifugal distortion constants for the two bands, and the Coriolis coupling constant, $\text{∥;ξ}{}_{28}{}^{\mathrm{c}}\text{∥; = 0.182 ± 0.015}\text{cm}{}^{\mathrm{?1}}$, have been determined.     

Thermal vibration in the cubic phase of K2SnCl6

The rectilinear and angular mean-square displacements of the atoms in K₂SnCl₆ have been measured from 293 to 450 K using single-crystal X-ray diffraction. The motion of the tin and chlorine atoms has been found to consist, essentially, of rigid-body translation and libration of the SnCl₆ octahedra. The root-mean-square angle of libration of the SnCl₆ octahedra, $\text{φ}{}^2$^{$\text{1}\text{2}$}, ranged from 5.7 to 6.1°. The slow variation of $\text{φ}{}^2$ with temperature, together with the measured non-zero value of one of the fourth cumulants of the chlorine atom displacement, are indicative of highly non-linear coupled motion associated with the soft-mode phase transition at 261.5 K.     

Predissociated rotational structure in the 2490-Å band of 15NO2

The rotational structure of the 000-000 band of the 2490-Å system of ¹⁵NO₂ ($\text{2}{}^2\text{B}{}_2\text{-}\text{X}\text{?}{}^2\text{A}{}_1$) has been analyzed from high dispersion grating spectrograph plates. The band is found to be slightly predissociated, exactly as in the ¹⁴NO₂ isotope, which suggests that it might be usable for laser separation of the isotopes of nitrogen; tables of the wavenumbers of the lines are given. The upper-state molecular constants are close to the values calculated by the isotope relations from those of ¹⁴NO₂.     

Absorption spectrum of BS2 at 4°K

BS₂, trapped in neon matrices at 4°K, exhibits extensive progressions in the A²Π_u ← X²Π_g and $\text{B}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{← X}{}^2\text{Π}{}_{\mathrm{g}}$ systems. From these transitions, those observed in the infrared, and a reinterpretation of gas-phase data, the following molecular constants (in solid neon) are obtained for linear symmetric ¹¹BS₂ (in cm^?1):

     

$\text{B}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$	T0 = 24,072	$\text{ν}{}_1\text{= 516}$
$\text{A}{}^2\text{Π}{}_{\mathrm{u}}$	T0 = 13.766	$\text{ν}{}_1\text{= 506}$
	A0 = ?263	$\text{ν}{}_2\text{= 311}$
		$\text{ν}{}_3\text{= 1535}$
$\text{X}{}^2\text{Π}{}_{\mathrm{g}}$	A0 = ?440	$\text{ν}{}_1\text{= 510}$
		$\text{ν}{}_2\text{= ～120}$
		$\text{ν}{}_3\text{= 1015}$