Three-dimensional organometallic thallium(I) supramolecular polymer nanostructures synthesized with sonochemical process

A new three-dimensional thallium(I) supramolecular polymer, [Tl₂(μ₂-ATA)]_n (1), [H₂ATA = 2-aminoterephthalic acid]_, has been synthesized and characterized. The single-crystal X-ray data of compound 1 shows one type of Tl^I ion with a low coordination number. Compound 1 was self-assembled from Tl⋯C, Tl⋯O and Tl⋯N secondary interactions in thallium(I) coordination and the active lone pair on Tl^I in this compound may be involved in donor bonding. Two sides of the aromatic ring of ATA²⁻ anion have been involved in two types of secondary Tl⋯C approaches. Three samples of 1 were synthesized with three different concentrations of initial reagents under ultrasonic irradiation. The thermal stability of compound 1 samples were studied by thermo gravimetric (TG) and differential thermal analyses (DTA). These nano-structures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM).     

Isotope shift measurements on the neutron-deficient thallium isotopes

Isotope shifts of the neutron-deficient thallium isotopes were measured on-line at the UNISOR mass separator. Spectroscopy was carried out using collinear fast beam laser spectroscopy in neutral thallium. The changes of the mean square charge radii were derived from the measurements. The changes in charge radii of the I=7 isotopes, including the newly measured¹⁸⁸Tl, are compared to the results in mercury and lead.     

Reflection spectra of (alkali metal,thallium (I), silver (I)) iridium (IV) hexachlorides

While the effect of rubidium and caesium ions in solid salts of IrCl₆ ^-- is a shift to lower wave-numbers, comparable to that occurring in organic solvents relative to water, the dark blue silver (I) and thallium (I) salts have a new, broad band in the red. Mixed crystals of Cs₂IrCl₆ and Tl₂IrCl₆ are prepared, and the absorption spectra are discussed in terms of a tendency to ‘ferroelectric rattling’ and strong covalent bonding of Ag and Tl. Analogous cases are pointed out in solid salts of other 5d-hexahalides.     

Laser spectroscopy of radioactive lead and thallium isotopes

By collincar fast beam laser spectroscopy hyperfine structure and isotope shift have been measured of neutron deficient radioactive isotopes of lead (¹⁹⁰Pb,¹⁹¹Pb,¹⁹²Pb,¹⁹³Pb,¹⁹⁴Pb,¹⁹⁵Pb,¹⁹⁶Pb,¹⁹⁷Pb) and thallium (¹⁸⁸Tl¹⁹⁰Tl,¹⁹¹Tl,¹⁹²Tl,¹⁹⁴Tl,¹⁹⁶Tl). Therefrom nuclear magnetic dipole moments, electric quadrupole moments, changes of the mean square charge radii and deformation parameters are deduced and compared with predictions from theory.     

On the origin of the visible emission in KBr:Tl and KCl:Tl crystals

The intensity of the visible emission of KBr:Tl at 440 nm is shown to increase linearly with the absorption in the A₁ band at 4.64 eV (267 nm). The latter band increased with the square of the Tl⁺ ions concentration, which supports its assignment to thallium dimers. Similarities in behavior between the 440 nm emission of KBr:Tl and the 475 nm emission of KCl:Tl suggest that the latter is also related to dimers. This is supported by the superlinear dependence of this emission on the Tl⁺ ion concentration. Deviations ofthe superlinearity from the square dependence expected for dimers is explained by the overlap between the weak dimer absorption and the very strong A-band.The 440 nm emission of KBr:Tl was found to be excited only in the A₁ component of the dimer absorption and not in the stronger A₂ component. This indicates that the emission process may be compound.     

Multiparticle photonuclear reactions in <Superscript>203</Superscript>Tl nuclei

The thallium isotopes ²⁰³Tl and ²⁰⁵Tl were irradiated using a beam of bremsstrahlung gamma quanta with the maximum energy E _γ ^m = 50 MeV from an RTM-70 electron racetrack microtron installed at the Scobeltsyn Nuclear Physics Research Institute (Lomonosov Moscow State University, Russia). The gamma spectra of the residual activity were measured for an irradiated sample. Photonuclear reactions in the ²⁰³Tl nuclei with emission from one to four neutrons were observed experimentally. The relative yields of the reactions ²⁰³Tl(γ,n)²⁰²Tl, ²⁰³Tl(γ,2n)²⁰¹Tl, ²⁰³Tl(γ,3n)²⁰⁰Tl, and ²⁰³Tl(γ,4n)¹⁹⁹Tl were determined for the first time.     

NMR study of both 19F and 205Tl motions in TlZrF5

Spin-lattice relaxation times in the laboratory T_l and rotating frames T_l? for both ¹⁹F and ²⁰⁵Tl nuclei were measured as a function of temperature. Comparison of the temperature dependence of longitudinal NMR relaxation rates of both ¹⁹F and ²⁰⁵Tl suggests that Tl⁺ ions are more mobile than F^? ones at high temperatures. Furthermore Fourier transform experiments show that two kinds of Tl⁺ ion can be distinguished at high temperatures, one of them being more mobile than the other one and probably responsible for the ionic conductivity of this material.     

A Tunneling Model for Afterglow Suppression in CsI:Tl,Sm Scintillation Materials

Combined radioluminescence, afterglow and thermoluminescence experiments on single-crystal samples of co-doped CsI:Tl,Sm suggest that samarium electron traps scavenge electrons from thallium traps and that electrons subsequently released by samarium recombine non-radiatively with trapped holes, thus suppressing afterglow. Experiments on single crystals support the inference that electrons tunnel freely between samarium ions and are trapped preferentially as substitutional Sm⁺ near V_KA(Tl⁺) centers where non-radiative recombination is the rate-limiting step. Afterglow in microcolumnar films of CsI:Tl,Sm is enhanced by inhomogeneities which impede tunneling between samarium ions, but is partly suppressed by annealing.     

Luminescence and defects creation under photoexcitation of CsI : Tl crystals in Tl-related absorption bands

Characteristics of the defects created at 4.2 K by the UV-irradiation of CsI : Tl crystals in the Tl⁺-related absorption bands (by photons of 5.8-4.8 eV energy) have been studied. The dependences of the intensities of the thermally stimulated luminescence peaks appearing near 60, 90 and 125 K and of the recombination luminescence photostimulation bands peaking at 2.35, 1.92, 1.33 and 0.89 eV on the irradiation energy and duration, uniaxial stress and thallium concentration have been examined. The mechanisms of the processes, responsible for the appearance of the intense visible (2.55 and 2.25 eV) luminescence of excitons localized near Tl⁺ ions and creation of defects pairs of the type of Tl⁰-V_K and Tl⁺-V_K with various distances between the components, have been discussed.     

Nuclear exchange coupling and electronic structure of low-dimensional semiconductors

We review the nuclear magnetic resonance (NMR) studies of the indirect nuclear exchange coupling and electronic structure of the chain and layered semiconductors Tl(I)M(III)X₂ (M = Tl, Ga, In, X = Se, S, Te) and some other low-dimensional Tl-contained semiconducting compounds. Both univalent and trivalent Tl atoms in these compounds show essential chemical shielding anisotropy despite their formal spherically symmetric 5d¹⁰6s² and 5d¹⁰ electron configurations. Such a behavior results from the sp-hybridization of the Tl electron wave functions. Strong exchange coupling among the spins of Tl¹⁺ and M³⁺ ions, which reside in neighboring chains or layers, is observed. Such coupling is realized due to the overlap of the Tl¹⁺ and M³⁺ electron wave functions across the intervening chalcogen atom. This overlap is the important mechanism in the formation of the valence and conduction bands and determines the electronic structure and properties of the compounds. The long-range indirect nuclear exchange coupling via a chalcogen atom is an analog of the Kramers mechanism of electron spin exchange via a nonmagnetic bridge ion. Recent photoemission spectroscopy studies and band-structure calculations of several aforementioned compounds have confirmed the NMR results on the interchain and interlayer overlap.     

Biasing effects on thallium and silver chlorides with dc/ac voltage

Comparison was made between crystals of thallium chloride and silver chloride on their biasing effects with dc/ac voltage. Previous reports say that, although their electrical conductivities are similar, the dominant charge carriers in the former are the Cl⁻ ions while the Ag⁺ ions in the latter. The present dc/ac study demonstrates the following: for thallium chloride, although Cl⁻ conduction may be dominant under low bias field, Tl⁺ conduction supercedes Cl⁻ conduction when the bias field is enhanced. For silver chloride, Ag⁺ conduction is overwhelming within wide temperature range, to cause easy dielectric breakdown on dc biasing. Concerning the extrinsic conductivity seen at temperatures below 60 °C (thallium chloride) or below 150 °C (silver chloride), it is ascribed to grain-boundary related electron conduction, not to grain-boundary related Tl⁺ or Ag⁺ conduction as reported earlier.     

Hyperfine structure and nuclear magnetic moments of some neutron-deficient thallium isotopes

Using the atomic-beam magnetic resonance method, hyperfine structure (h.f.s.) measurements have been performed in the²P_1/2 electronic ground state of the neutron-deficient thallium isotopes^193–202Tl. In the doubly odd isotopes, the magnetic dipole hyperfine interaction constantsa were determined, while in the odd-A isotopes, direct measurements of the nuclearg-factors,g _I , were made. The electronicg-factor was measured in¹⁹⁸Tl. The magnetic dipole moments of the doubly odd isotopes have been evaluated by a direct comparison with known values in the stable isotope²⁰³Tl. The moments of the odd-A isotopes are in agreement with pervious measurements by optical spectroscopy. A discussion of the magnetic dipole moments in terms of different nuclear models is included. The moments of the 2^? nuclear ground states of the doubly odd isotopes may be interpreted as arising from a combination of the configurations 2^? (πs_1/2 vf_5/2) and 2^? (πs_1/2 vp_3/2).     

Superdeformed bands in195Tl

Two superdeformed (SD) bands have been found and assigned to¹⁹⁵Tl on the basis of excitation function and cross bombardment results. The two bands are almost identical in transition energies to those observed in¹⁹³Tl. They are signature partners with a splitting, presumably due to the proton i_13/2 (=5/2) orbital, characteristic of all known SD bands in the thallium isotopes. Their alignments relative to the¹⁹³Tl bands were found to be zero.On leave from Comision National de Energia Atomica 1429 Buenos Aires, Argentina.     

Nuclear moments of the neutron-deficient thallium isotopes

The nuclear moments of the neutron-deficient^187,188Tl isotopes were determined by measuring the hyperfine structure splittings of the λ=535 nm line in neutral thallium. An optical efficiency of 2×10⁻⁴ photons per radioactive ion was achieved using collinear fast beam laser spectroscopy with a large solid angle fiber optical array detector. Most of the moments can be interpreted fairly well in the single particle model.     

Sorption Technique of Separation of Thallium-201 from Proton-Irradiated Thallium

A sorption technique is developed for radiochemical separation of thallium-201 from proton-irradiated targets of metallic thallium. The technique consists in separation of ²⁰¹Pb with the PbSO₄ precipitate followed by separation of ²⁰¹Pb and ²⁰¹Tl in the column with ammonium 12-molybdophosphate fixed in the matrix of porous Teflon (AMP-sorbent). The chemical yield of radiothalium is 98%, the duration of chemical procedures is 2.5 … 3 hours.     

Nuclear moments and the change in the mean square charge radius of neutron deficient thallium isotopes

The hyperfine structure, isotope and isomeric shifts in the atomic transition 6p ² P _3/2–7s ² S _1/2, =535 nm have been measured for theI=7 andI=2 states of^{190, 192, 194, 196}Tl; theI=1/2 andI=9/2 states of¹⁹¹Tl and the I=7 isomer of¹⁸⁸Tl. The thallium isotopes were prepared as fast atomic beams at the GSI on-line mass separator following fusion reactions and — in some cases — subsequent-decay. The nuclear dipole moments, electric quadrupole moments and the change in the nuclear mean square charge radius are evaluated. Theuu-isotopes show an isomeric shift which changes sign between¹⁹²Tl and¹⁹⁴Tl.Dedicated to P. Armbruster on the occasion of his 60th birthday     

Observation of α-decay in thallium nuclei,including the new isotopes 184Tl and 185Tl

With the use of an on-line isototpe separator α-decay was observed for the first time in thallium nuclides, including the new isotopes ¹⁸⁴Tl and ¹⁸⁵Tl. Their identification has led to the observation of the 0⁺ deformed band head in ¹⁸⁴Hg and allows for the possibility of determining whether ¹⁸⁵Hg is deformed in its ground state.     

Selective excitation of the 62 D 3/2 state of the atomic thallium beam

The absorption of the tunable narrow-band laser radiation with λ = 276.9 nm at the 6² P _1/2 → 62 D _3/2 transition in the atomic thallium beam is experimentally studied. The isotopic selectivity and efficiency of the excitation of the 6² D _3/2 state is investigated. The splittings between the ²⁰³Tl and ²⁰⁵Tl isotopes were found to be Δv = 0.98 and 1.25 GHz for the transitions with the nuclear momenta F = 1 → F = 1, 2 and F = 0 → F = 1, respectively, which is sufficient for a relatively high isotopic selectivity of the 6² D _3/2 state excitation with the subsequent ionization for the laser separation of the thallium isotopes. The effects that lead to the broadening of the resonance and a decrease in the selectivity are analyzed. The main contribution is related to the field broadening by the laser radiation, which limits the mean laser power density.     

Isotopic dependence of giant multipole resonances

A procedure is presented which allows the application of linear response theory and the random phase approximation to an open shell. The procedure is applied to Ca isotopes. The general features of giant multipole resonances are found to vary smoothly with the mass. The resonances exhibit more structure in the open 1f_{$\text{7}\text{2}$} shell nuclei. While the energy-weighted dipole sum is practically constant in all isotopes, the isoscalar quadrupole and octupole energy weighted sums increase continuously by ~ 30 % from ⁴⁰Ca to ⁴⁸Ca.     

Alpha decay of new neutron deficient gold,mercury, and thallium isotopes

In fusion evaporation reactions of a⁹²Mo beam with targets of neutron deficient Rb — Mo isotopes very neutron deficient isotopes of elements between Au and Po have been produced. The new isotopes^{173, 174}Au,^{175, 176}Hg, and¹⁷⁹Tl were identified by alpha spectroscopy. The mass excess value of¹⁷⁶Hg could be linked to known values of theN?Z=16 chain. The location of the new isotopes with respect to the proton drip line is discussed. A new high energyα transition of (7.20±0.02) MeV andT _1/2=(1.4±0.5) ms has been found in the reaction⁹²Mo+⁸⁹Y→¹⁸¹Tl^* at an excitation energy of 37 MeV. It is tentatively assigned to isotopes produced in 2-particle evaporation channels.