EPR and optical study of Mn doped ammonium oxalate monohydrate

Studies on fine and hyperfine structures of paramagnetic resonance spectra in single crystals of Mn²⁺: ammonium oxalate monohydrate are reported. As sufficient numbers of lines were not obtained at room temperature, measurements have been done at liquid nitrogen temperature and at the frequency of X-band. The Mn²⁺ spin Hamiltonian parameters have been evaluated employing a large number of resonant line positions observed for various orientations of the external magnetic field and the surrounding crystalline field has been discussed. The values of the zero field parameters that give good fit to the observed EPR spectra have been evaluated. The values obtained for g, A, B, D, E and a are 2.0002±0.0002, (100±2)×10⁻⁴, (79.5±2)×10⁻⁴, (257±2)×10⁻⁴, (85±2)×10⁻⁴ and (−18±1)×10⁻⁴ cm⁻¹, respectively. The percentage of covalency of the metal-ligand bond is also determined. The optical absorption study has been done at room temperature. The observed bands are assigned as transitions from the ⁶A_1g(S) ground state to various excited quartet levels of Mn²⁺ ion in a cubic crystalline field. The electron repulsion parameters (B and C), the crystal field splitting parameter(Dq) and the Trees correction (α) providing good fit to the observed optical spectra have been estimated and the values obtained for the parameters are B=897, C=2144, Dq=910 and α=76 cm⁻¹.     

EPR and optical absorption study of Cr doped diammonium hexaaqua magnesium sulphate single crystal

EPR measurements of Cr³⁺ doped diammonium hexaaqua magnesium sulphate single crystals are made at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular orientations. The value of g=1.9763±0.0002 and are evaluated. On the basis of EPR data the site symmetry of Cr³⁺ in the crystal is discussed. Optical absorption studies of single crystals are also carried out at room temperature. The orbital energies of the chromium ion are estimated from the optical absorption spectrum. The different bonding parameters are obtained by correlating optical and EPR data and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are obtained as B=676,C=3371, , h=1.258 and k=0.21.     

ESR of Cu doped cadmium (II) formate dihydrate

Electron spin resonance (ESR) of Cu²⁺ doped cadmium formate dihydrate single crystal was studied at room temperature. Copper enters the lattice substitutionally and is trapped at two magnetically inequivalent sites. The observed spectra are fitted to a spin-Hamiltonian of rhombic symmetry with the following values of the spin-Hamiltonian parameters, Cu²⁺(I): g_x=2.097±0.002, g_y=2.1166±0.002, g_z=2.2887±0.002 and A_x=(140±2)×10⁻⁴ cm⁻¹, A_y=(151±2)×10⁻⁴ cm⁻¹, A_z=(239±2)×10⁻⁴ cm⁻¹, Cu²⁺(II): g_x=2.0843±0.002, g_y=2.1045±0.002, g_z=2.2742±0.002 and A_x=(141±2)×10⁻⁴ cm⁻¹, A_y=(158±2)×10⁻⁴ cm⁻¹, A_z=(267±2)×10⁻⁴ cm⁻¹. The ground state wave function of the Cu²⁺ ion in this lattice is evaluated. It is found that the ground state is predominantly |x²−y²〉. The g-factor anisotropy is also calculated and compared with the experimental value. With the help of the optical absorption study, the nature of bonding in the complex has been discussed.     

EMR and optical study of Mn2+ doped potassium trihydrogen selenite

The EMR study of Mn2+ doped potassium trihydrogen selenite is performed and the site of Mn2+ in the lattice is discussed. The zero field parameters providing good fit to the observed EMR spectra are estimated. The spin-Hamiltonian parameters g, A, B, D, and a are (2.0003 +/- 0.0002), (31 +/- 2) x 10(-4), (20 +/- 2) x 10(-4), (87 +/- 2) x 10(-4), and (-9 +/- 1) x 10(-4) cm(-1), respectively. The percentage of covalency of the metal-ligand bond is also determined. The optical absorption study suggests the lattice distortion in the crystal. The electron repulsion and crystal field parameters having good fit to the observed optical spectra are evaluated. The band positions are fitted with the Racah parameters (B and C), the cubic crystal field splitting parameters (Dq), and the Trees correction (alpha). The values of B, C, Dq, and alpha are 871, 2967, 670, and 76 cm(-1), respectively.     

ESR and optical study of Cu-doped Bis(l-asparaginato)zinc(II)

The Electron spin resonance (ESR) study of Cu²⁺-doped Bis(l-asparaginato)zinc(II) has been done at room temperature. Two magnetically equivalent sites for Cu²⁺ have been observed. The spin-Hamiltonian parameters evaluated with the fitting of spectra to rhombic symmetry crystalline field are g_x=2.0341±0.0002, g_y=2.0649±0.0002, g_z=2.2390±0.0002, A_x=(51±2)×10⁻⁴ cm⁻¹, A_y=(75±2)×10⁻⁴ cm⁻¹and A_z=(169±2)×10⁻⁴ cm⁻¹. The ground state wave function of Cu²⁺ has also been determined. The g-anisotropy has been estimated and compared with the experimental value. Further with the help of optical study, the nature of bonding of metal ion with different ligands in the complex has been discussed.     

EPR and optical absorption studies of vanadyl impurity in zinc potassium phosphate hexahydrate single crystal

Electron paramagnetic resonance (EPR) study of VO²⁺ doped zinc potassium phosphate hexahydrate single crystal is carried out. The angular variation of the spectra is studied in the three crystallographic planes. The principal value of spin Hamiltonian parameters g and A and the direction cosines which principal axes make with the crystallographic axes are determined. The observed values are site I: g_∥=1.9664±0.0002, g_⊥=1.9973±0.0002, A_∥=150±2×10⁻⁴, A_⊥=60±2×10⁻⁴ cm⁻¹; site II: g_∥=1.9276±0.0002, g_⊥=1.9921±0.0002, A_∥=155±2×10⁻⁴ and A_⊥=62±2×10⁻⁴ cm⁻¹. By comparison of direction cosines of g from EPR with the direction cosines of different bonds obtained from crystal structure data it is ascertained that the VO²⁺ ion occupies Zn²⁺ substitutional sites. The optical absorption study of the crystal at room temperature is also carried out. The bands observed in the optical absorption spectrum are attributed to d-d transitions. The EPR results together with the optical data are employed to estimate the molecular orbital (MO) coefficients. These MO coefficients (also called bonding coefficients) are further used to discuss the nature of bonding of VO²⁺ ion with different ligands in the crystal.     

EPR and optical absorption study of Cr-doped ammonium oxalate monohydrate single crystals

The electron paramagnetic resonance (EPR) study of the Cr³⁺-doped ammonium oxalate monohydrate (AOM) single crystal is done at room temperature. Two magnetically inequivalent sites for chromium are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The spin Hamiltonian parameters are evaluated as: D=(309±2)×10⁻⁴ cm⁻¹, E=(103±2)×10⁻⁴ cm⁻¹, g=1.9820±0.0002, A=(161±2)×10⁻⁴ cm⁻¹ for site I and D=(309±2)×10⁻⁴ cm⁻¹, E=(103±2)×10⁻⁴ cm⁻¹, g=1.9791±0.0002, A=(160±2)×10⁻⁴ cm⁻¹ for site II, respectively. On the basis of EPR data the site symmetry of Cr³⁺ doped single crystal is discussed. The optical absorption spectra are recorded in 195-925 nm wavelength range at room temperature. The energy values of different orbital levels are determined. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The values of different parameters are B=803, C=3531, D_q=2208 cm⁻¹, h=0.59 and k=0.21, where B and C are Racah parameters, D_q is crystal field parameter and h and k are nephelauxetic parameters, respectively.     

EPR and optical absorption study of Cr-doped tetramethyl ammonium cadmium chloride single crystals

EPR study of Cr³⁺-doped tetramethyl cadmium chloride (TMCC) single crystals is carried out at room temperature. The crystal field and spin-Hamiltonian parameters are evaluated from the resonance line positions of different lines observed in the EPR spectra. The g and D parameter values are found to be g=1.9741±0.0002 and D=553±2×10⁻⁴ cm⁻¹, respectively. EPR data indicate that the site symmetry of Cr³⁺ ion in the crystal is distorted octahedron. Cr³⁺ ions enter the lattice substitutionally replacing Cd²⁺ sites and bind to the neighboring extra Cd vacancies necessary for charge compensation. The optical absorption spectra are measured in 195–925 nm wavelength range at room temperature. From optical study the energy values of different orbital levels are estimated. Further, the bonding parameters are obtained by correlating optical and EPR data and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are obtained to be B=722, C=2845, Dq=2043 cm⁻¹, h=1.015 and k=0.21.     

ESR investigation of Cr diffusion in MgO powders

The electron spin resonance (ESR) technique was used to investigate the diffusion of Cr³⁺ in magnesium oxide (MgO) powders. The ESR absorption intensity was measured for several annealing times and four different temperatures of isothermal annealing: 1223, 1273, 1323 and 1373 K. The activation temperature for diffusion, calculated from the experimental data using a theoretical model based on the Fick equation, was found to be E_A=212±9 kJ mol⁻¹. This result is about 30% smaller than similar data obtained for single-crystal MgO using the radioactive-tracer sectioning technique. The difference is attributed to a higher concentration of defects in the powder relative to single crystals.     

Growth, EPR and optical absorption spectra of l-threonine single crystals doped with Cu ions

We investigated the crystal growth, electron paramagnetic resonance (EPR) and optical absorption spectra of l-threonine doped with Cu²⁺. The quality, size and habit of the single crystals grown from aqueous solution by the slow solvent evaporation and by the cooling methods vary when the impurities are introduced during the growth process. The variations with the magnetic field orientation of the EPR spectra of single-crystal samples at room temperature and 9.77 GHz in three crystal planes (ab, bc and ac) show the presence of copper impurities in four symmetry-related sites of the unit cell. These spectra display well resolved hyperfine couplings of the of Cu²⁺ with the I_Cu= of the copper nuclei. Additional hyperfine splittings, well-resolved only for specific orientations of the magnetic field, indicate that the copper impurity ions in the interstitial sites have two N ligands with similar hyperfine couplings. The principal values of the g and A_Cu tensors calculated from the EPR data are g₁=2.051(1), g₂=2.062(2), g₃=2.260(2), A_Cu,1=16.9(5)×10⁻⁴ cm⁻¹, A_Cu,2=21.8(6)×10⁻⁴ cm⁻¹, A_Cu,3=180.0(5)×10⁻⁴ cm⁻¹. The principal directions corresponding to g₃ and to A_Cu,3 are coincident within the experimental errors, reflecting the orientation of the bonding planes of the copper ions in the crystal. The values of the crystal field energies are evaluated from the optical absorption spectrum, and the crystal field and bonding parameters of the Cu impurities in the crystal are calculated and analyzed. The EPR and optical absorption results are discussed in terms of the crystal structure of l-threonine and the electronic structure of the Cu²⁺ ions, and compared with data reported for other systems. The effects of the impurities in the growth and habit of the crystals are also discussed.     

EPR and optical study of Mn-doped bis(l-Asparaginato)Zn(II)

EPR and optical studies of single crystals of Mn²⁺: bis(l-Asparaginato)Zn(II) are reported. The spin-Hamiltonian parameters are determined employing the positions of a large number of resonance lines for various orientations of the external magnetic field. The best-fit zero-field parameters to the observed EPR spectra are obtained as, D=(228±2)×10⁻⁴ cm⁻¹, E=(58±2)×10⁻⁴ cm⁻¹ and a=(−12±1)×10⁻⁴ cm⁻¹,whereas g=2.0002±0.0002, , and . From the optical absorption study, the lattice distortion is suggested. The electron repulsion parameters (B and C) and crystal field parameters (Dq and α) evaluated from the fitting of observed optical spectra are: B=858 cm⁻¹, C=2620 cm⁻¹, Dq=950 cm⁻¹, and α=76 cm⁻¹.     

EPR and optical absorption studies on VO ions in zinc lactate trihydrate

EPR and optical absorption studies of VO²⁺-doped zinc lactate trihydrate single crystals are done at room temperature. The EPR spectra of VO²⁺ are characteristic of tetragonally compressed octahedral site. The angular variation of the EPR spectra shows single site occupying interstitial position in the lattice. The spin Hamiltonian parameters are evaluated as g_x=1.9771, g_y=2.0229, g_z=1.9236 and A_x=76, A_y=104, A_z=197 (×10⁻⁴) cm⁻¹. Using these parameters and optical absorption data various bonding parameters are determined and the nature of bonding in the complex is discussed.     

Dynamical Jahn-Teller distortion in single crystals of Cu(II) doped magnesium potassium phosphate hexahydrate: a variable temperature EPR study

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II)-doped magnesium potassium phosphate hexahydrate have been carried out at room temperature. The temperature dependence of g and A values has been obtained for the polycrystalline sample and the ground state is unambiguously identified. These results indicate the existence of a dynamic Jahn-Teller distortion for Cu(II) ion. The g and A tensor direction cosines are evaluated and compared with Mg-O directions, which confirms that Cu(II) enters substitutionally in the lattice.     

Structural and optical properties of Mn doped ZnS semiconductor nanostructures

Manganese doped zinc sulphide nanoparticles were fabricated by adopting an inexpensive solution growth route. Different samples were fabricated by varying Mn concentrations. UV-VIS study reveals blue-shift on the onset of absorption and hence enhancement in the optical band gap upto 0.75 eV, indicating strong quantum confinement. Photoluminescene study for all the samples display characteristic band edge peak at ∼410 nm. The broad peak ∼560–580 nm is ascribed to Mn incorporation. Further, structural investigations were carried out by using X-Ray diffraction and transmission electron microscopy (TEM).     

Mn掺杂ZnO薄膜的结构及光学性能研究

通过脉冲激光沉积(PLD)法在SiO₂基片上制备了不同含量的Mn掺杂ZnO薄膜.X射线衍射、X射线能谱、原子力显微镜与紫外-可见分光光度计测试结果表明：少量的Mn离子的掺杂并没有改变薄膜的结构，薄膜具有(103)面的择优取向；PLD法制备的ZnO薄膜的成分与靶材基本一致，实现了薄膜的同组分沉积；薄膜表面比较平坦，起伏度小于80nm，颗粒尺寸主要集中在25nm附近；但是Mn离子的掺杂改变了ZnO薄膜的禁带宽度，随Mn掺杂含量的增加，ZnO薄膜的禁带宽度增加；当薄膜中Mn含量从6%增加到 关键词： PLD ZnO薄膜 Mn掺杂 吸收谱     

Synthesis and optical characterization of monodispersed Mn doped CdS nanoparticles

Monodispersed Mn²⁺ doped CdS nanoparticles with average size as small as 1.8 nm have been synthesized through chemical method. The nanostructures of the prepared nanoparticles have been confirmed through X-ray diffraction (XRD), ultraviolet-visible (UV-vis) absorption and transmission electron microscope (TEM) measurements. The photoluminescence emission covering 450-650 nm of the visible region is observed under ultraviolet light excitation, from Mn²⁺ doped CdS nanoparticles dispersed in dimethyl sulfoxide (DMSO).     

Effect of rare earth radius and concentration on the structural and transport properties of doped Mn–Zn ferrite

Dielectric constant (ε′), AC conductivity (σ), and seebeck coefficient (S) have been measured for the ferrite samples of the general formula Mn_0.5Zn_0.5R_yFe₂O₄; where R=Dy, Gd, Sm, Ce, and La prepared by standard ceramic technique and sintered at 1200 °C with a heating rate 4 °C/min. X-ray diffractograms show that all samples posses the spinel structure with the appearance of small peaks representing secondary phases. There is a lowering in the porosity starting after Sm-doped samples due to the presence of the secondary phases, which limits the grain growth. Due to seebeck measurements the manganese–zinc (Mn–Zn) ferrite doped with the rare earth has been classified as P-type semiconductors. It is possible to increase the electrical resistivity by using a small quantity of Dy³⁺ ions substitutions owing to the structural heterogeneity generated by the insulating intergranular layers. The isolation of the grains is the most promising approaches for further reduction in the eddy current losses at the operating frequencies.     

第一性原理研究Al掺杂Mn4Si7的电子结构及光学性质

基于密度泛函理论框架下,利用第一性原理计算方法,对本征Mn₄Si₇以及不同Al掺杂浓度下Mn₄Si₇的电子结构及光学性质进行系统计算分析. Mn₄Si₇晶胞中有16个Mn原子及28个Si原子,建立4种Mn_16-xAl_xSi₂₈(x=0,2,4,8)的掺杂模型,计算结果表明：本征Mn₄Si₇的禁带宽度E_g =0.775 eV,属于间接带隙半导体,Al的掺入导致了Mn₄Si₇费米能级附近的电子结构发生改变,导带向低能方向发生偏移,价带向高能方向发生偏移,禁带宽度由0.775 eV降至零,呈现出金属性.计算还表明,在光子能量低能区域,Al的掺入使Mn₄Si₇的介电函数、折射率、吸收及反射系数等光学性质有所提升,改善了Mn₄S...     

第一性原理研究B掺杂Mn_4Si_7的电子结构和光学性质

采用基于密度泛函理论的第一性原理计算方法,对未掺杂及B掺杂Mn_4Si_7的电子结构和光学性质进行理论计算.研究结果表明,未掺杂Mn_4Si_7是间接带隙半导体,其禁带宽度为0.786 eV,B掺杂后其禁带宽度下降为0.723 eV. B掺杂Mn_4Si_7是p型半导体材料.未掺杂Mn_4Si_7在近红外区的吸收系数达到10~5 cm~(-1),B掺杂引起Mn_4Si_7的折射率、吸收系数、反射系数及光电导率增加.