A program for simulation of powder-type EPR spectra

An algorithm of a computer program for simulation of powder type EPR spectra (S=1/2,I≠0) is described. For determination of the energy levels, the perturbation approach is used and corrections up to second order due to hyperfine, quadrupole, and nuclear Zeeman coupling are taken into account. No restrictions on the mutual orientations of the eigenvectors ofg, hyperfine, and quadrupole tensors are imposed. Simulated spectra for a model paramagnetic system (S=1/2,I=3/2) with axial symmetry and noncoinciding directions ofg _‖ andA _‖ are presented.     

Nucleic acid spin labeling study of interaction between polyadenylic acid: Polyuridilic acid duplex and egg phosphatidylcholine vesicles. Involvement of terminal and internal nucleotides and sugar-phosphate backbone

Model DNA-membrane contacts were studied in the system containing polyadenylic acid (polyA): polyuridilic acid (polyU) duplex and egg phosphatidylcholine (PC) vesicles without or in the presence of MgCl₂. PolyU containing O-(1-oxyl-2,2,5,5-tetramethylpyrroline-3-carbonyl) spin label at 2′-OH moiety was used for spin labeling study of nucleic acid-phospholipid interactions. For polyA labeled with the same nitroxyl radical EPR spectra from spin labels attached at terminal and at internal nucleotide units contribute into the EPR spectrum of d.s. polynucleotide without or in the presence of egg PC vesicles and Mg ions. Internal spin labels are more sensitive to the interaction with PC-MLV than terminal ones. The complexation between s.s. polynucleotide and PC-MLV was shown. The values of spin labels’ melting temperature of polyA: SL-polyU duplex at 1 mM MgCl₂ reflect the changes in rotational mobility of terminal spin labels connected with duplex→triplex transition. Arrhenius plots of temperature dependence of EPR spectra parameters prove that ribose moieties of sugarphosphate backbone are involved into the interaction between polynucleotide duplex and phospholipid bilayer. Egg PC vesicles demonstrate stabilizing effect on polyA: polyU duplex at 1 mM of Mg²⁺ and destabilizing effect at 5 mM Mg²⁺.     

An ENDOR study of radical spin adducts derived from novel 2-substituted-5,5-dimethyl-pyrroline-N-oxide spin traps

ENDOR spectra of a series of carbon- and oxygen-centered radical adducts of 2-substituted DMPO-type nitrones are reported. They include the novel cyclic nitrones, 2-phenyl-5,5-dimethyl-pyrroline-N-oxide (2-Ph-5,5-M₂PO), 2,5,5-trimethyl-l-pyrroline-N-oxide (2,5,5-M₃PO), and 2-phenyl-3,3,5,5,-tetramethyl-l-pyrroline-N-oxide (2-Ph-3,3,5,5-M₄PO). Electron paramagnetic resonance (EPR) was used to ascertain the nitrogen hyperfine splittings (hfs’s) while¹H ENDOR was employed to determine the long-range (γ) hydrogen hfs’s. The magnitude of the nitrogen hfs combined with the numbers and sizes of the long-range γ-H hfs’s of spin adducts of these new spin traps are shown to help disclose the identities of various added radicals (or radical addends). It should be noted that the three new spin traps presented here are keto-nitrones not aldo-nitrones. Thus, there is alkyl (e.g. CH₃) or aryl (e.g. C₆H₅) substitution at the 2-position of the pyrroline-N-oxide ring. This feature is part of our search for modified spin traps that yield spin adducts with greater stability.     

Far-infrared photoconductivity spectra of quenched-in acceptors in Germanium: absorption and photo-thermal ionization lines of two new shallow acceptors

The far-infrared photoconductivity spectra of germanium crystals quenched from T>800C show three new sets of hydrogenic acceptor excitation lines, in addition to the 8.69 meV (SA^'₁) and 9.48 meV (SA^“₁) acceptor series reported earlier. The corresponding ground state binding energies are 13.89 meV (SA^'₂), 14.42 meV (SA^“₂), and 17.89 meV (SA₃). We tentatively attribute both the SA^'₂ and the SA^“₂ line series to one acceptor complex with a multiple ground state. At high acceptor concentrations the excitation lines are seen as sharp minima superimposed on a continuous photoconductivity background. With decreasing acceptor concentration, or increasing temperature, they gradually evolve into the familiar positive-going photo-thermal ionization peaks. This is explained by the different concentration and temperature dependence of the cross-sections for the absorption and photo-thermal ionization mechanisms.     

Complex acceptors in CdTe:Cl investigated by differential spectroscopy

The acceptor states in CdTe:Cl single crystals are investigated using a technique based on the analysis of differential spectra of selectively excited donor-acceptor pair photoluminescence. The splitting of 2P _3/2(Γ₈) and 2S _3/2(Γ₈) states of the Ag_Cd tetrahedral acceptor taking place upon a decrease in the donor-acceptor separation is found. The energies of seven excited states of the complex acceptor with an activation energy of ～121 meV are determined.     

EPR study of carbonate derived and ozonide radicals in carbonated apatites synthesized from aqueous solutions

In this study, a series of Na⁺ and¹²CO ₃ ^2? containing apatites synthesized by a hydrolysis of octo-calciumphosphate (OCP) and dried at 25°C until constant weight, were examined with EPR after X-irradiation. A variety of different paramagnetic radicals was formed, giving rise to composite and hence complex EPR powder spectra. The spectra were successfully decomposed into their basic components using a multivariate statistical technique. The different components could be identified unambiguously. In this way, it was found that an O^?, an O ₃ ^? , a CO ₃ ^? , two types of CO ₂ ^? and two types of CO ₃ ^3? ions were formed upon X-irradiation. Also resonances from atomic hydrogen were observed. The most striking feature is the presence of the ozonide ion, which is only rarely observed in irradiated hydroxyapatites. A comparison is made between the EPR spectra of apatite samples prepared by hydrolysis of OCP on the one hand, and those of samples prepared by hydrolyzing monetite, and the tooth enamel spectrum on the other hand.     

ESR study of Cu(II)-indomethacin and its pyridine and DMF adducts

Powder ESR spectra of [Cu₂(Ind)₄](H₂O)₂ at room temperature show the presence of copper acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J≈?338 cm^?1). Two different monomeric species were evidenced in 40%Py+60%DMF solution absorbed on NaY zeolite: the Cu(Ind)₂(DMF)₂ with an elongated tetragonal-octahedral symmetry and the Cu(Ind)₂(Py)₂ with a CuN₂O₂ chromophore in atrans square-planar arrangement. Only one monomeric species Cu(Ind)₂(Py)₂ was identified in 20%Py+80%DMF and 20%Py+80% Chloroform solutions. The Cu(Py)₄ ²⁺ species of CuN₄ chromophore occurs in pyridine Cu(II)-indomethacin solution suggesting a decomposition of the solvit compound.     

Synthesis and optical properties of N-In codoped ZnO nanobelts

N-In codoped ZnO nanobelts were successfully synthesized via high-temperature chemical vapor deposition for the first time, using the mixture of In/ZnO as a precursor. The EDX spectrum showed that In was introduced into ZnO nanobelts. In order to better understand the optical properties of N-In codoped ZnO nanobelts, the Raman and low-temperature PL spectra of the undoped, In-doped and N-In codoped ZnO nanostructures were measured. By contrasting, N is incorporated into the nanobelts. The temperature dependent photoluminescence (PL) spectra were investigated. Their PL spectra in the temperature from 9 K to room temperature were dominated by an A^oX emission of excitons bound to 2No-In_Zn acceptor complexes. The dissociation energy of the acceptor complexes is estimated to be 89-112 meV.     

Spectroscopic Studies of the Reactions of π-Electron Acceptors with the Cyclic Polyamine 1,4,8,11-Tetraazacyclotetradecane

The reactions of π-electron acceptors such as 1-chloro-2,4,6-trinitrobenzene (picryl chloride), 7,7′,8,8′-tetracyanoquino-dimethane (TCNQ), tetrachloro-p-benzoquinone (chloranil) and tetra-cyanoethylene (TCNE) with the cyclic polyamine base 1,4,8,11-tetraazacyclotetradecane (TACTD) have been investigated in CHCl₃ solvent. The data indicate the formation of the CT-complexes with the general formula [(TACTD) (acceptor)₂]. The 1: 2 stoichiometry of the (TACTD)-acceptor was based on elemental analysis and infrared spectra of the solid CT-complexes along with the photometric titration curves for the reactions in CHCl₃. The formation constants (K) for the CT-complexes are shown to be strongly dependent on the type and structure of the acceptor.     

Orientation of the imidazole type ligands in copper complexes studied by ESEEM

Effects of nitrogen quadrupole coupling tensors on ESEEM spectra are discussed. It is shown from theoretical considerations that the spectra, especially the double quantum transition line, are strongly affected by changes of tensor orientation in the magnetic field. Model calculations for angle-selected nitrogen ESEEM spectra of copper complexes in the disordered state show that the double quantum transition line changes its intensity with the resonance magnetic field set position in the EPR spectrum. These model calculations also show that estimation of the orientation of the imidazole type ligands with respect to theg principal axes may be easily made without any tedious processes of computer simulation of the whole ESEEM spectral pattern. The usefulness of the method is experimentally shown by applying it to the structural studies of the copper complexes of 2-(2′-pyridyl)imidazole and 2(2′-pyridyl) benzimidazole and their six coordinated complexes with nitrogeneous bases.     

Optical properties of p-type ZnO doped by lithium and nitrogen

A lithium and nitrogen doped p-type ZnO (denoted as ZnO: (Li, N)) film was prepared by RF-magnetron sputtering and post annealing techniques with c-Al₂O₃ as substrate. Its transmittance was measured to be above 95%. Three dominant emission bands were observed at 3.311, 3.219 and 3.346 eV, respectively, in the 80 K photoluminescence (PL) spectrum of the p-type ZnO:(Li, N), and are attributed to radiative electron transition from conduction band to a Li_Zn-N complex acceptor level (eFA), radiative recombination of a donor-acceptor pair and recombination of the Li_Zn-N complex acceptor bound exciton, respectively, based on temperature-dependent and excitation intensity-dependent PL measurement results. The Li_Zn-N complex acceptor level was estimated to be about 126 meV above the valence band by fitting the eFA data obtained in the temperature-dependent PL spectra.     

Photoluminescence and recombination centers in phosphorus-doped and undoped CdTe heat-treated under component vapour pressures

Photoluminescence spectra in heat-treated CdTe : P and undoped CdTe were studied at temperatures of 4.2–77 K in the edge emission and the exciton emission region. Temperature dependences and excitation intensity dependences were measured, and the recombination mechanism of each emission line was identified. A change in recombination centers with p_Cd was studied. In a heavily doped crystal an acceptor A₂ (66 meV) was dominant at low p_Cd and the phosphorus acceptor (78 meV) at high p_Cd. A rather deep donor (about 35 meV) was also observed. In a lightly doped crystal the spectra were intermediate between those of the undoped and the heavily doped crystas, and the emission line due to the phosphorus acceptor was not observed. In an undoped crystal an acceptor A₁ (52 meV) was dominat at low p_Cd and the A₂ acceptor at medium and high p_Cd.     

Luminescence of CuInS2: I. The broad band emission and its dependence on the defect chemistry

The emission of CuInS₂ is studied as a function of the exact composition in terms of deviations from molecularity and stoichiometry. By means of temperature-dependent (4.2–220 K) and excitation-intensity-dependent measurements, the two broad emission bands usually present are correlated with donor-acceptor transitions. In In-rich material the acceptor is located at 0.10 eV above the valence band. This acceptor is ascribed to V_Cu. In Cu-rich CuInS₂ the acceptor level is located at 0.15 eV above the valence band, which is attributed to either V_In or Cu_In. Two donor levels are identified, their ionization energies being about 35 and 72 meV. These donors are present in both In and Cu-rich samples and may originate from either intrinsic defects or impurities (Fe). Also, the influence of quenching of the crystals as well as the effect of different crystal growth methods (melt-growth and vapour-growth) on the emission is studied.     

The effect of temperature on the photoluminescence ofp-CuGaSe2 single crystals

We studied the temperature dependences of spectral bands and of the outer quantum yield of the edge photoluminescence (PhL) of p-CuGaSe₂ single crystals obtained by the method of chemical transport reactions. We determined the activation energies of acceptor levels and showed that the temperature dependence of the intensity of PhL is determined by an acceptor level of 35 meV below the Debye temperature and of 150 meV above the Debye temperature. The spectra of the edge PhL at 300 and 80 K are determined mainly by band-band optical transitions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 4, pp. 590–593, July–August, 1998.     

Effect of annealing in N2 atmosphere on net acceptor concentration in ZnSe:N grown by MOCVD

Annealing effect on net acceptor concentration in ZnSe:N is investigated. ZnSe:N homo-epitaxial layer was grown at 823 K by MOCVD using ammonia (NH₃) as a dopant source. Photoluminescence (PL) spectra measured on as-grown layer exhibited the strong deep donor–acceptor pair (D^dAP) emission and the weak I₁^N emission line. In order to enhance the activation of nitrogen in ZnSe epitaxial layer, sample was annealed at the 823 K in nitrogen (N₂) and hydrogen (H₂) atmosphere. Only the annealing in nitrogen atmosphere increased I₁^N emission intensity indicate the activation of nitrogen acceptor. And net acceptor concentration was estimated to be 3 × 10¹⁷cm⁻³ by C–V measurements. This activation mechanism is interpreted as hydrogen is released from N–H bonds during annealing in nitrogen atmosphere.     

Observation of broad EPR spectra of transient free radicals by FT-EPR

Application of electron spin echo Fourier transform EPR (ESE-FT-EPR) to photo-induced chemical reactions is presented. Main purpose of this study is to observe broad EPR spectra of free radicals having very shortT ₂ ^* by means of the ESE-FT-EPR technique. Details of the experimental procedures are described. In ESE experiments design of the resonator is important to obtain sufficient spectral bandwidth because of use of multiple pulses which decrease the bandwidth. We designed and constructed Loop-Gap-Resonantors (LGR) for light irradiation experiments and their specifications were examined. The phase cycling method is essential to obtain pure ESE signals and proper time resolution by eliminating unwanted FID signals which result from imperfect pulse angles. We applied this technique to observe the photo-induced electron transfer reaction between tetraphenylporphinato zinc(II) (ZnTPP) and duroquinone (DQ) in an ethanol solution, and successfully observed the time resolved EPR spectra of the both Zn(TPP) cation and DQ anion radicals by ESE-FT-EPR of the Hahn echo. The half-height full-width of envelope of EPR spectrum of Zn(TPP)⁺, which is never observed in ordinary FT-EPR, is about 16 MHz. Specificity of spectra and the time resolution are compared among the ESE-FT-, FT- and cw-Time-Resolved-EPR (cw-TREPR) techniques.     

Luminescence of mercuric iodide crystals

Low-temperature (4.2–130 K) photoluminescence spectra of HgI₂ crystals have been measured in the 540–700 nm region. An analysis of the characteristics (intensity vs temperature and excitation power relations, afterglow times, excitation spectra) of the 560, 620, and 635 nm emission bands suggests the following assignments: the 560 nm band is due to radiative annihilation of excitons bound to mercury vacancies, and the “red” emission originates from recombination of free (620 nm) and donor-localized (635 nm) electrons with a hole-filled acceptor level. The energies of the corresponding donor and acceptor levels have been estimated. New emission bands at 540, 545, and 575 nm have been discovered, and their origin discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 67–73 (January 1997)     

High resolution magneto-optical studies of p-InSb

High resolution photoconductivity and transmission spectra in p-InSb are obtained over a wide temperature range at magnetic fields from 9 to 100 kG using a CO₂ laser. The low temperature results are described in terms of hole transitions from the acceptor ground state to excited states associated with free light-hole Landau states.     

Impurity effects on the magnetization and magnetic susceptibility of an electron confined in a quantum ring under the presence of an external magnetic field

The magnetization and the magnetic susceptibility of a single electron confined in a two-dimensional (2D) parabolic quantum ring under the effect of external uniform magnetic field and in the presence of an acceptor impurity have been studied. The shifted 1/N expansion method was used to solve the Hamiltonian quantum ring within the effective mass approximation. The computed energy spectra, the magnetization and magnetic susceptibility have been displayed as a function of the quantum ring parameters: confinement strength ω₀, magnetic field strength (ω_c), and temperature (T). The obtained energy results show level-crossings, in the absence and presence of acceptor impurity, which are manifested as oscillations in the magnetization and magnetic susceptibility curves.     

Acceptor excited states in indium phosphide

Selective donon-acceptor pair luminescence and luminescence excitation spectra reveal acceptor excitations to all excited states of principal quantum number 2, odd as well as even parity. These transition energies are independent of the D-A pair separation R for sufficiently large R and are then identical to those on isolated acceptors. However, they decrease significantly at small R and some splittings are revealed in our measurements on a bulk grown crystal in which the most common contaminant acceptor Zn is dominant. The p state transition energies are used together with the known ionization energy of the Zn acceptor to derive valence band parameters for InP according to the theory of Baldereschi and Lipari. We find γ₁ = 5.6 ± 0.7, γ₂ = 2.0 ± 0.3, γ₃ = 2.4 ± 0.3, where γ₁ is adjusted to fit the cyclotron resonance data of Leotin et al. Some reservations concerning the completeness of this theory are acknowledge. Information on the s acceptor excited state is consistent with that obtained from acceptor bound exciton “two-hole” satellites for this remarkable quality bulk crystal.