Laser time-resolved selective excitation of Nd3+ ions in KNdP4O12 crystals

The emission spectra of Nd³⁺ ions in KNd_xRE_1?xP₄O₁₂ (RE = Y, La and Pr) and KNd_xCr_1?xP₄O₁₂ crystals were investigated. Under selective excitation into ²G$\text{7}\text{2}$ + ⁴G$\text{5}\text{2}$ multiples at 1.6 K the fluorescence of Nd³⁺ ions in non-equivalent crystal sites was observed. The excitation spectrum of the ${}^4\text{F}\text{3}\text{2}$ fluorescence had a complex satellite structure. Time resolved measurements showed the dependence of the fluorescence decay on the excitation wavelength. Selective excitation into the satellite lines at the wings of the main transition led to strongly non-exponential decay. The low temperature results indicated that there is no spectral energy transfer between ions in different types of sites.     

Magnetic field dependent optical dephasing in LaF3:Er3+

Optical dephasing of the 5388 Å transition between the lowest Kramers doublets of the ⁴S_{$\text{3}\text{2}$} and ⁴I_{$\text{15}\text{2}$} multiplets of Er³⁺:LaF₃ has been studied by photon echo, optical phase switching and optical free induction decay. Er³⁺?¹⁹F hyperfine interactions produce dephasing which is two orders of magnitude faster than in previously studied non-Kramers systems, but at high field changes in the spin dynamics result in microsecond dephasing. For the lower Zeeman component of ⁴S_{$\text{3}\text{2}$}, T₂ (=6μs) is independent of H₀ whereas for the upper component the dephasing is rapid and strongly field dependent. This is quantitatively accounted for by spin lattice relaxation of the upper component of ⁴S_{$\text{3}\text{2}$}. Below 20 kG concentration and temperature dependent dephasing due to electron spin diffusion is observed.     

Crystal field splittings and luminescence properties for Nd3+, Er3+ and Dy3+ in yttrium orthoaluminate (YAlO3)

This report contains information appropriate for a theoretical analysis of the optical spectra of triply ionized lanthanides in YAlO₃. Starting with the best-fit crystal field parameters, the crystal field splitting schemes, multiplet-to-multiplet line strengths, radiative lifetimes, branching ratios, line-to-line square matrix elements and g-factors for the triply ionized Nd, Er and Dy in YAlO₃ have been calculated. In this paper detailed discussions were made on the luminescence properties of the principal transitions of Nd-doped YAlO₃ emanating from the metastable ⁴F_{$\text{3}\text{2}$} state to Stark components of multiplets of the ground ⁴I_J term and compared to similar results of Y₃Al₅O₁₂ (YAG). The line-to-line branching ratios were calculated including J-mixing effects. In the calculations, only electric dipole transitions were considered because of odd-parity. The results predicted some interesting differences in the optical behavior of Nd³⁺ in these two host materials. It has been observed that there is a reasonable agreement between the theoretical data and those reported experimentally for YAlO₃ and YAG. The theoretical studies undertaken here were chosen to supplement or extend the optical data for these two host materials.     

Analysis of the B1Πu → X1Σg+ band system of 7Li2 molecule excited by the 4545- and 5287-Å visible lines of the argon ion laser

Two new fluorescence series have been excited by the two lines at the extreme ends of the range of visible Ar⁺ transitions, 4545 and 5287 Å. In each case the B¹Π_u electronic state of ⁷Li₂ is excited, to levels $\text{v′ = 12, J′ = 13 (4545}\text{A}\text{?}\text{)}$ and $\text{v′ = 2, J′ = 58 (5287}\text{A}\text{?}\text{)}$. Fluorescence to the ground state can be detected in the range 2 ≤ v″ ≤ 23 and 0 ≤ v″ ≤ 8, respectively. Measured relative intensities agree well with calculated radiative transition probabilities reported herein.     

V4+ in SrTiO3: A Jahn-Teller impurity

EPR results of V⁴⁺, with $\text{S =}\text{1}\text{2}$, in SrTiO₃ are reported. The tetragonal local symmetry of the impurity ion is related to strong T_2g × ?_g coupling as evidenced by intensity variations in the presence of stress. At 4.2 K the V⁴⁺ EPR behaviour is related to the intrinsic local strain in SrTiO₃.     

EPR,thermoluminescence, and thermally stimulated conductivity in BaWO4 crystals

In BaWO₄ crystals electrons and holes trapped at WO₄ complexes are identified by electron paramagnetic resonance (EPR) after X-irradiation at T = 80 K. The thermal decay of the intrinsic hole centres at about 100 K is accompanied by a simultaneous decrease of electron traps (WO₄)^3- and glow maxima of thermoluminescence (TL) and of thermally stimulated conductivity (TSC). This connection is explained by a thermally activated hopping of the $\text{(WO}{}_4\text{)}\text{3-}\text{2}$ hole centres followed by radiative recombination with electron traps (WO₄)^3-. A qualitative kinetic calculation based upon EPR data and the shift between TL and TSC glow peak confirms this model.     

The crystal structures of the ion conductors (NH+4)Zr2(PO4)3and (H3O+)Zr2(PO4)3

The crystal structures of (NH⁺₄)Zr₂(PO₄)₃ and (H₃O⁺)Zr₂(PO₄)₃ have been determined from neutron time-of-flight powder diffraction data obtained at 15 K. Both compounds are rhombohedral, $\text{R}\text{3}\text{c}$, with cell parameters a=8.7088(1) and c=24.2197(4) Å for the ammonium compound and a=8.7528(2), c=23.6833(11) Å for the hydronium compound. In both cases the ions are completely localized in the type I cavities and hydrogen bonded to lattice oxygens. The measured unit cell parameters are relatively large for this class of compounds but the entrance ways into the cavities are still too small to allow for unrestricted movement of the ions. Thus the low conductivity of the hydronium ion is related to this and other structural features.     

Gamow-Teller resonance in β+ decay of 147mDy and spin-isospin current renormalization

The total absorption spectrum of γ-rays following β⁺ decay of ^147mDy has been investigated. The decay energy Q_ε = 7.18 (10) MeV and an improved value of half-life $\text{T}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= 55.7 (7)}\text{s}$ are determined. The intensity of the transitions from the isomeric state is 31 (3)%, the internal conversion being included. More than 40% of decays populate ¹⁴⁷Tb levels with the excitation energy E_ex ? 4.4 MeV. The β⁺ strength function S_β⁺ exhibits a pronounced narrow maximum at E_ex = 4.84 MeV and some structure at higher energy. The total probability of ^147mDy β⁺ decay corresponds to the value $\text{log}\text{?t = 3.67 (8)}$.The calculation of S_β carried out in the random-phase approximation gives the correct resonance energy. The coefficient of the spin-isospin current renormalization found from the comparison of the calculated β-decay probability with the experimental one is |;G_A/g_v|; = 0.7±0.1.     

Observation of electronic Raman transitions from the transition metal ions Ti3+ and V4+ highly diluted in α-Al2O3

α-Al₂O₃ : Ti³⁺ (300 mass ppm concentration) at 10 K shows two electronic Raman transitions at 38 cm^-1 and 109 cm^-1. The E symmetry of the scattering matrix agrees with the selection rules for transitions between the ground state B_{$\text{3}\text{2}$} and the E_{$\text{1}\text{2}$} of the ground state manifold ²t_2g.α-Al₂o₃ : V⁴⁺ shows two very weak electronic Raman transitions at about 30 cm^-1 and 56 cm^-1 respectively.     

Transition moment variation in the A2Σ+ → X2Πi transition of HCl+, DCl+ and HBr+

Relative emission intensities of sixteen bands of HCl⁺ (A²Σ⁺ - X²Π_i), four bands of DCl⁺ (A²Σ⁺ - X²Π_i), and 5 bands of HBr⁺ (A²Σ - X²Π_i) have been made using both ion-beam excitation and microwave discharge sources. Intensities were determined by comparison with computer-generated spectra. Treatment of the data within the r-centroid approximation shows that in HCl⁺ the electronic transition moment decreases strongly at large $\text{r}{}_{\mathrm{v\prime v″}}$ [$\text{Re}\text{α}\text{exp}\text{(?3.6}\text{r}{}_{\mathrm{v\prime v″}}\text{)}\text{for 1.44}\text{A}\text{?}\text{< r}{}_{\mathrm{v\prime v″}}\text{< 1.82}\text{A}\text{?}$] but levels off at shorter $\text{r}{}_{\mathrm{v\prime v″}}$. DCl⁺ data agree quantitatively with HCl⁺. The variation in the HBr⁺ moment is similar, with $\text{R}\text{e}\text{α}\text{exp}\text{[?4.5}\text{r}{}_{\mathrm{v\prime v″}}\text{]}\text{for 1.58}\text{A}\text{?}\text{<}\text{r}{}_{\mathrm{v\prime v″}}\text{< 1.78}\text{A}\text{?}$.     

High-resolution laser spectroscopy of the Swan system (d3Πg-a3Πu) of C2 in an organic halide-alkali metal flame

The 0–1 band of the Swan system (d³Π_g-a³Π_u) of C₂ has been recorded by laser-induced fluorescence of C₂ formed by reaction between Na and C₂Cl₄. Most of the spectrum was recorded at Doppler-limited resolution, but overlapped lines were resolved using sub-Doppler techniques. The Q branches of the $\text{ΔΩ = 0}$ subbands and rotational lines for which $\text{ΔΩ = ±1}$ are observed for the first time. Molecular parameters defined in the effective Hamiltonian of Brown and Merer are obtained for both ³Π states.     

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.     

Mise en évidence d'un échange électronique entre Fe2+ ET Fe3+ dans les oxydes rhomboédriques AFe2O4 par spectroscopie mossbauer DU57Fe

The ABB'O₄ rhomboedral oxides containing exclusively either Fe²⁺(InFeGe_0,5Zn_0,5O₄) or Fe³⁺(LuMg-FeO₄ and LuMnFeO₄) are investigated with Mössbauer spectroscopy, in their paramagnetic state.A similar study is made on two mixed oxides containing iron under its two oxidation states, with the $\text{Fe}{}^{\mathrm{2+}}\text{Fe}{}^{\mathrm{3+}}\text{= 2}$ and 1 (InFe_1,5Ga_0,5O₄ and InFe₂O₄) atomic ratio.Comparing the results, we have come to the conclusion that a fast electronic exchange between Fe²⁺ and Fe³⁺ takes place at room temperature. In this structure, point Fe²⁺ and Fe³⁺ are distributed on the same crystallographic site with the point symmetry C_3v. We show that neighbouring effects lower this local symmetry.     

Polarization spectroscopy of the E0g+-B0u+ band system of Br2

The E-B (0_g⁺-0_u⁺) band system of Br₂ has been investigated at Doppler-limited resolution using polarization labeling spectroscopy. Merged E state data for the three naturally occurring isotopes in the range v_E = 0–16, expressed in terms of the constants for ⁷⁹Br₂, are (in cm^?1) Y_0,0 = 49 777.962(54), Y_1,0 = 150.834(22), Y_2,0 = ?0.4182(28), Y_3,0 = 6.6(11) × 10^?4, Y_0,1 = 4.1876(28) × 10^?2, Y_1,1 = ?1.607(16) × 10^?4, and Y_0,2 = 1.39(39) × 10^?8. The bond distance is $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.194}\text{A}\text{?}$, and the diabatic dissociation energy to $\text{Br}{}^{\mathrm{+}}\text{(}{}^3\text{P}{}_2\text{) +}\text{Br}{}^{\mathrm{?}}\text{(}{}^1\text{S}{}_0\text{)}\text{is 34 700 cm}{}^{\mathrm{?1}}$.     

The emission spectra of H35Cl+, H37Cl+, D35Cl+, and D37Cl+ in the region 2700–4100 Å

The $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}\text{-X}{}^2\text{Π}$ emission spectrum of HCl⁺ has been measured and analyzed for four isotopic combinations. These analyses extend previous work and provide rotational constants for the v = 0–2 levels of the ground state and for the v = 0–9 levels of the excited state. RKR potentials have been determined for both states, although the upper state could not be fitted precisely to such a model. Calculated relative intensities based on these potentials demonstrated that the electronic transition moment must change rapidly with lower state vibrational quantum number. Although considerable caution should be exercised in applying the concept of equilibrium constants to the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state, the following are the best estimates of these constants (in cm^?1) for the $\text{X}{}^2\text{Π}$ state of H³⁵Cl⁺: B_e = 9.9406, ω_e = 2673.7, A_e = ? 643.7, and $\text{r}{}_{\mathrm{e}}\text{= 1.315}\text{A}\text{?}$. For the $\text{A}{}^2\text{Σ}{}^{\mathrm{+}}$ state of H³⁵Cl: T_e = 28 628.08, B_e ～ 7.505, ω_e ～ 1606.5, and $\text{r}{}_{\mathrm{e}}\text{= 1.514}\text{A}\text{?}$.     

The ionic distribution in Mn2+ and Zn2+ β″-alumina

The ionic distributions in Mn²⁺ and Zn²⁺ β″-alumina (idealized formula: $\text{X}{}_{\mathrm{<mtext>5</mtext><mtext>6</mtext>}}\text{Mg}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{Al}{}_{\mathrm{<mtext>31</mtext><mtext>3</mtext>}}\text{O}{}_{17}\text{;}\text{X}\text{=}\text{Mn}\text{and}\text{Zn}\text{)}$ at 296 K are reported from single-crystal X-ray diffraction studies. Mn²⁺ β″-alumina exhibits the shortest c-axis found so far in any divalent β″-alumina: 33.141(3) Å;Zn²⁺ β″-alumina, which involves the smallest divalent ion studied in the frame-work, has a considerably longer c-axis: 33.517(3) Å. Both compounds show clear evidence of short-range correlation effects in the X²⁺ ion arrangement by way of departures from the centrosymmetric space-group $\text{R}\text{3}\text{m}$ of the β″-skeleton. Both 6c end-sites and 9d mO-sites ($\text{R}\text{3}\text{m}$ notation) are occupied for both ion-types, a significantly larger occupation (60% compared to 28% of the total) lying at or near the 9d mid-oxygen sites in Mn²⁺ β″-alumina compared to Zn²⁺ β″-alumina. Disorder is also found in the column-oxygen O(5) in both cases; the O(5) displacement from the 3b site in Mn²⁺ β″-alumina (0.59 Å) is the largest found in any divalent β″-alumina. The formula-unit/cell-layer, deduced on the basis of the amounts of X²⁺ ions refined, and assuming charge compensation through Mg substitution alone, are: Mn_0.79Mg_0.57Al_10.43O₁₇ and Zn_0.87Mg_0.74Al_10.26O₁₇.     

Spin dynamics in the impurity-doped one-dimensional heisenberg paramagnet (CH3)4NMn(1-x)CuXCl3: Nuclear magnetic relaxation

Proton spin-lattice relaxation rate has been measured at room temperature in the impurity-doped (CH₃)₄NMn_(1-x)Cu_xCl₃ for X = 0.04, 0.1 and 0.17. The result for Hz. snfc;chain-axis as a function of resonance frequency clearly shows that the spectral density of the spin fluctuations in the impure system remains to have the characteristics 1-D diffusive term (ω^{-$\text{1}\text{2}$}), with a slower rate of the spin diffusion in accordance with the theory by Richards. The result for H⊥ chain-axis indicates, however, the existence of a singularity of the fluctuations near ω = 0.     

Rotational analysis of the B3Π(0+) → X1Σ+ band systems of 35Cl35Cl and 35Cl37Cl in the chlorine afterglow emission spectrum

The B³Π(0⁺) → X¹Σ⁺ band system of Cl₂, excited by the recombination of ground state $\text{Cl}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ atoms at total pressures near 2 Torr, has been rotationally analyzed in the range 6300–9900 Å. About 30 bands, with 0 ≤ v′ ≤ 6 and 5 ≤ v″ ≤ 14, were investigated, mostly for both ³⁵Cl³⁵Cl and ³⁵Cl³⁷Cl. The band origins and rotational constants for the B state were obtained with the help of the known constants for the ground state. The principal molecular constants (cm^?1) for the B³Π(0⁺) state of ³⁵Cl³⁵Cl are as follows: T_e′ = 17 817.67(3); ω_e′ = 255.38(3); ω_e′x_e′ = 4.59(1); ω_e′y_e′ = ?0.038(8); D_e′ = 3341.17(14); B_e′ = 0.16313(3); α_e′ = 2.42(3) × 10^?3; γ_e′ = ?5.7(7) × 10^?5. The equilibrium internuclear separation is 2.4311(2) Å. The results of Briggs and Norrish on a transient absorption spectrum of Cl₂ assigned as $\text{0}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{← B}{}^3\text{Π}\text{(0}{}^{\mathrm{+}}\text{)}$ are reinterpreted with the present constants.     

Long-lived non-equilibrium population of Fe3+ electronic states after the K-capture of 57Co

Mössbauer emission spectra of a frozen aqueous solution of ⁵⁷CoCl₂ show contributions from the $\text{S}{}_{\mathrm{z}}\text{= +}\text{5}\text{2}$ and the $\text{S}{}_{\mathrm{z}}\text{= +}\text{3}\text{2}$ Zeeman levels of Fe³⁺ ions at T = 4.2 K in H ? 30 kG. The K-capture results in a non-equilibrium state of relaxation time comparable to the lifetime of the nuclear excited state (～ 10^?7 s).     

Crystal growth,structure, electron paramagnetic resonance and magnetic properties of (NH4)2V3O8

A method to grow single crystals of ammonium vanadate (IV, V) (NH₄)₂V₃O₈ has been devised. The crystal structure is tetragonal P4bm; residual factor is R = 0.030. Cell parameters are $\text{a = 8.891 ± 0.004}\text{A}\text{?}$ and $\text{c = 5.582 + 0.002}\text{A}\text{?}$. The V⁵⁺ atom lies at the center of a triangular pyramide (VO₄ tetrahedron) while the V⁴⁺ atom is on A 4-fold rotation axis at the center of a square-based pyramide VO₅ whose symmetry point group is almost C_4v with the short V = O bond lying along the 4-fold axis parallel to the c edge of the tetragonal cell. Crystals are thin platlets with (001) cleavage planes. The platlets have very often a square or rectangular shape limited by {100} or {110} planes. Each single crystal was not large enough to record a good e.p.r. spectrum, but by sticking on the same quartz plate a score of them it was possible to gather enough crystals so to record correct spectra and by orienting the plate to obtain resonance lines separately for g_∥ = 1.9263 et g_τ = 1.9755. Measurements at 283 K on powder samples gave times for spin-spin relaxation T₂ = 0.4 × 10^?7s and for spin-lattice relaxation T₁ = 1.6 × 10^?7s. The magnetic structure is characterized by an exchange narrowing ω_e = 3 × 10¹⁰rad/s which corresponds to a transition temperature of about 0.5 K. Static susceptibility measurements at high magnetic field show a paramagnetic behaviour with an antiferromagnetic interaction which is interpreted in the magnetic space group P_2c4bm as the interaction between V⁴⁺ ions from consecutive planes parallel to (001).