Superhyperfine structure of the EPR spectra of Ce<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The EPR spectra of Ce³⁺ impurity ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals have been investigated at a frequency of ∼9.3 GHz in the temperature range 5–25 K. The effective g factors of the ground Kramers doublet of the cerium ions in three crystals are close to each other (g _‖ = 2.737, g _⊥ = 1.475 for LiYF₄:Ce³⁺). A superhyperfine structure of the EPR spectrum of Ce³⁺ ions in the LiTmF₄ Van Vleck paramagnet has been observed in the external magnetic field B oriented along the crystallographic axis c (B ‖ c). The superhyperfine structure of the EPR soectra of the Ce³⁺ ions in the LiYF₄ and LiLuF₄ diamagnetic matrices is resolved for B ⊥ c. Possible factors responsible for this pronounced difference in the properties of the systems studied have been discussed.     

Effect of doping on the magnetic properties of the low-dimensional antiferromagnet CuO

The effect of doping with Li⁺, Zn²⁺, Ni²⁺, and Ga³⁺ ions on the magnetic susceptibility of the low-dimensional antiferromagnet CuO (T _N=230 K) has been studied within a broad temperature range of 77–600 K. The solubility of impurity ions in the CuO lattice is low, ⩽3%. Impurity ions, similar to intrinsic defects, distort antiferromagnetic coupling and can shift the long-and short-range magnetic-order regions toward lower T. Fiz. Tverd. Tela (St. Petersburg) 40, 1876–1880 (October 1998)     

Synthesis of Highly Selective Indole-Based Sensors for Mercuric Ion

Two indole-based fluorescent chemosensors 1 and 2 were prepared and investigated characteristic features with transition metal ions. Sensors 1 and 2 were selective for Hg²⁺ ion, among a series of metal ions, in aqueous ethanol (H₂O–EtOH, 1:2, v/v) with association constants of 5.74 × 10³ and 4.46 × 10³ M⁻¹ and detection limits of 7.4 and 6.8 μM, respectively. Computational results revealed that sensor 1 or 2 with Hg²⁺ ion formed 1:1 complex with a central, sandwich-coordinated Hg²⁺ ion. Computational calculations provided evidence that a sandwich-coordinated Hg²⁺ ion center was formed and the polyoxyethylene spacer acted as a scaffold for bringing functional ligands into a suitable geometry.     

Jahn-Teller effect on Sm3+ ions in SmB6

Electron spin resonance on samarium ions with stabilized valence Sm³⁺ is investigated in the fluctuating-valence semiconductor SmB₆, both pure and doped with the rare-earth ions Eu²⁺, Er³⁺, and Gd₃₊. The dynamic and static Jahn-Teller effects have been observed for the first time on rare-earth ions. The relation between the Jahn-Teller effect in a fluctuating-valence semiconductor and the excitonic nature of the ground state of such a semiconductor is discussed. Zh. éksp. Teor. Fiz. 115, 1860–1871 (May 1999)     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

Decay of an electronic vortex of a collisionless shock wave as a possible mechanism of a “Coulomb explosion”

A new mechanism of a “Coulomb explosion,” where ions are accelerated by the electric field separating charges at the magnetic Debye radius r _B∼B/4πen _e, is proposed on the basis of a nonquasineutral model of electronic vortices in a magnetic field. It is shown by means of numerical calculations that in the process of acceleration of the ions a collisionless shock wave, whose front has an effective width of the order of δ∼r _B, determined by the breakdown of quasineutrality, is formed in a time of the order of ω _pi ⁻¹ , where ω_pi is the ion plasma frequency. The origin of such explosive dynamics is the formation of “holes” in the electron density at characteristic times of the order of ω _pe ⁻¹ (ω_pe is the electronic plasma frequency) as a result of the generation of electronic vorticity by the Weibel instability of an electromagnetic wave. Calculations for a laser pulse with intensity J∼6×10¹⁸ W/cm² show that the ions expand in the radial direction with velocities up to 3.5×10⁸ cm/s. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 10, 669–674 (25 November 1999)     

Photo-induced reactions of hemin (DMSO) n clusters (n = 0-3) produced with electrospray ionization

Photo-induced reaction of [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with dimethylsulfoxide (DMSO) is investigated by using a tandem mass spectrometer with electrospray ionization. We measure the photodissociation yields of mass-selected hemin⁺(DMSO)_n clusters for n = 0-3 in the energy region of 15 800-28 200 cm^-1. The mass spectra of the fragment ions show the β-cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules. Yield of the β-cleavage reaction is found to depend strongly on the excitation energy and the number of solvent molecules. We also examine the metastable decomposition of the clusters following primary mass selection and determine the incremental solvent binding energies and internal energies for the clusters using evaporative ensemble model. From these results, we investigate the reaction mechanism of β-cleavage of hemin⁺ ion.     

Magnetooptical method of measuring the characteristics of the reservoir of spin-spin interactions in paramagnets

Based on the phenomenon of coherent spin Raman scattering a magnetooptical method of measuring the characteristics of the reservoir of electronic spin-spin interactions in paramagnets was implemented. A formula relating the intensity of the inelastically scattered light to the temperature of the spin-spin reservoirs under conditions of saturation of the EPR of paramagnetic ions has been derived. For the Ce³⁺ ions in the (Ce_xLa_1−x)₂Mg₃(NO₃)₁₂·24H₂O crystal values of the time of spin-lattice relaxation of the spin-spin reservoir and the local magnetic field have been measured, and a relation between the spin-spin reservoir temperature and the external magnetic field strength under conditions of stationary saturation of the EPR of the Ce³⁺ ions has been obtained. V. I. Ul’yanov-Lenin Kazan State University,18, Lenin St., Kazan, 420008, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 76–81, January–February, 1997.     

Spin-spin interaction of Ni2+ ions in ZnSiF6·6H2O

The angular dependences of the electron spin resonance spectrum of 1% Ni²⁺ ions in a ZnSiF₆·6H₂O matrix are investigated experimentally at 36 GHz and 4.2 K. Besides the main spectrum of the isolated ion, we observed a spectrum due to interacting pairs of Ni²⁺ ions, located in the first (nn) and second (2n) coordination spheres and coupled by, besides the magnetic dipole-dipole interaction, isotropic exchange: J _nn = (−197±1)×10⁻⁴, J _2nα = (−5±1)×10⁻⁴, and J _2nβ = (3±2)×10⁻⁴ cm⁻¹. Lines due to other isolated Ni²⁺ ions, which have a different initial splitting D, are also present in the spectrum with intensity comparable to the pair spectrum. Low-symmetry distortions of the crystal field are observed, caused by a pair of impurity ions located close to one another. It is shown that the previously proposed interpretation is incorrect. Fiz. Tverd. Tela (St. Petersburg) 41, 1602–1608 (September 1999)     

Dispersion of the Voigt effect in the magnetic semiconductors Cd1−x MnxTe

Spectral measurements of the Voigt birefringence Δn were performed for the cubic magnetic semiconductor Cd_1−x Mn _x Te (0≤x≤0.52) in order to investigate how the exchange interaction of Mn²⁺ ions with itinerant electrons depends on the electron wave vector. It was determined that Δn/x ² is independent of x and the magnetic field direction, i.e., the effect is due to the Mn²⁺ ions and is isotropic. Below the band gap edge the dispersion of the birefringence Δn can be described well in all samples by the unusual dependence Δn∼(E _g −ℏω) ^−3.5. This can be explained by a decrease of the exchange interaction of Mn²⁺ ions with itinerant electrons with increasing distance from the center of the Brillouin zone. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 8, 569–573 (25 April 1998)     

A Simple and Neutral Receptor Acting as a Sensitive and Switch-on Fluorescent Chemosensor for H<Subscript>2</Subscript>PO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack>

A novel artificial anion chemosensor 1 based on 2, 2′-di (4-nitrophenylurea-β-N-yl) -1, 1′-binaphthyl is designed and synthesized for sensing anions including halide ions and oxoanions. The fluorescent emission of the binaphthyl of receptor 1, forming the hydrogen bonding with anions as the sensing mechanism, is monitored in DMSO for detecting anions. In brief, while most of the anion chemosensors are switch-off fluorescent chemosensor, or non-fluorescent sensor, receptor 1 exhibits obviously the switch-on emission during the complexation with H₂PO₄⁻.     

EPR study of exchange interactions in the nonmagnetic Kondo system La1−x CexCu6

The EPR of paramagnetic impurities Gd³⁺ and Mn²⁺ was studied in nonmagnetic Kondo system La_1−x Ce_xCu₆ containing in the 1.6–200 K range. The exchange interaction parameters of gadolinium and manganese ions with conduction electrons, of cerium ions with conduction electrons and with one another, the Kondo temperature of cerium ions, and the temperature behavior of cerium-ion spin-fluctuation rate have been determined. A pseudogap in the density of states at the Fermi level has been detected in the CeCu₆ regular system, which is apparently due to s-f hybridization. This pseudogap can be destroyed by introducing an aluminum impurity, which induces strong conduction-electron scattering. It was also found that RKKY interaction among manganese ions in CeCu_6−y Mn_y is considerably stronger than it is in LaCu_6−y Mn_y, which implies enhancement of nonlocal spin susceptibility due to an f band contribution to conduction-electron states. Fiz. Tverd. Tela (St. Petersburg) 40, 593–599 (April 1998)     

Optical spectra of triply-charged rare-earth ions in polycrystalline corundum

Solid samples of polycrystalline corundum α-Al₂O₃ activated by triply-charged rare-earth ions RE³⁺ (R=Eu³⁺, Er³⁺, Pr³⁺) were synthesized by the sol-gel technology. Characteristic narrow-line optical absorption and luminescence spectra produced by intraconfigurational 4f-4f transitions in RE³⁺ ions have been measured. RE³⁺ ions have been established to form one dominant type of optical centers in the corundum matrix, and the energy diagram of Eu³⁺ and Er³⁺ Stark levels in corundum has been determined. Fiz. Tverd. Tela (St. Petersburg) 40, 1442–1449 (August 1998)     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Electron multiplicity in slow collisions of Ar ions with C

Electron capture by Ar⁸⁺ in collisions with C₆₀ fullerene has been investigated using coincident measurements of the number n of ejected electrons, the mass and charge of multicharged Cr+ ₆₀ recoil ions and their fragments Ci+ m and the final charge state of outgoing projectiles Ar(8-s)+ (). The number of captured electrons r is the sum of the numbers of stabilized and emitted electrons: r = n + s. The ratio n / s decreases by a factor three with s increasing from 1 to 7 showing that the multiply excited states populated by capture of a large number of electrons are rather stable against auto-ionisation. Each kinetic energy spectrum of Ar⁺ and Ar²⁺ projectiles is composed of two peaks which we attribute to collisions “inside” and “outside” the C₆₀ cage. The measured energy shift of the projectile keV is consistent with the corresponding energy loss keV in a carbon foil with an equivalent thickness. Inside collisions are characterized by a strong dissociation of recoil ions into light monocharged fragments and by a high multiplicity of ejected electrons. Received: 25 March 1998 / Received in final form and Accepted: 9 June 1998     

Superhyperfine structure of the EPR spectra of Nd<Superscript>3+</Superscript> and U<Superscript>3+</Superscript> ions in Li<Emphasis Type="Italic">R</Emphasis>F<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Y,Lu, Tm) double fluorides

The superhyperfine structure of the EPR spectra of impurity Nd³⁺ and U³⁺ ions in LiYF₄, LiLuF₄, and LiTmF₄ double-fluoride single crystals has been observed and discussed. In LiYF₄: Nd (g _| = 1.987, g _⊥ = 2.554) and LiTmF₄: Nd, the superhyperfine structure is observed at the orientation of the external magnetic field B in parallel to the c axis of the crystals and consists of nine components with a splitting of ∼15.4 MHz. In LiYF₄: U (g _| = 1.149, g _⊥ = 2.508) and LiLuF₄: U, the superhyperfine structure is observed at both B | c and B ⊥ c and consists of nine and eleven components, respectively, with a splitting of ∼21.5MHz. It should be noted that the resolution of the superhyperfine structure of the EPR spectrum of LiLuF₄: U³⁺ becomes significantly higher with a deviation from the orientation B ⊥ c.     

Experimental investigations of the formation of XeF*(B 2II1/2) excimer molecules during the injection of SF6 into a xenon plasma flow

The luminescence of XeF*(B ²II_1/2) molecules from a zone formed in the injection of SF₆ gas into a freely flowing xenon plasma jet is investigated. The experiments show that both the energy characteristics of the luminescence and the geometrical dimensions of the plasmachemical reaction zone can be controlled by varying the power input to the plasmatron and the mass flow rates of SF₆ and the xenon plasma. It is shown that the main contribution to the production of XeF*(B ²II_1/2) excimer molecules under the given experimental conditions is from two-particle ion-ion reactions involving Xe ions and SF ₆ ⁻ and SF ₅ ⁻ molecular ions. Zh. Tekh. Fiz. 68, 36–42 (February 1998)     

Centers of charge nonuniformity and reduction of copper oxide CuO during irradiation with nitrogen ions

Long-range reduction of CuO to Cu₂O and Cu was observed by irradiating polycrystals and different planes of CuO single crystals ((110) and (020)) with 16-MeV nitrogen ions with fluence 10¹⁷ cm⁻². The infrared absorption spectra show an increase in the number of hole [CuO₄]⁵⁻ and electronic [CuO₄]⁷⁻ centers. The highest density of electronic centers and reduction occur near the surfaces of the samples. Fiz. Tverd. Tela (St. Petersburg) 41, 1564–1567 (September 1999)