Yb：YAG晶体中的色心

在用引上法生长的Ｙｂ：ＹＡＧ晶体中，存在一个独特的色心，其吸收带位于３７５ｎｍ的６２５ｎｍ，随着Ｙｂ２Ｏ３掺杂浓度的增加，色心浓度增加，探讨了晶体生长过程中色心形成机理。高强γ射线辐照Ｙｂ：ＹＡＧ晶体，诱导大量色心的形成。晶体中的 对激发态Ｙｂ＾３＋离子的荧光寿命具有流淬火效应，因此，Ｙｂ：ＹＡＧ激光晶体需要经高温退火，消除色心的影响。     

色心晶体及激光研究进展

色心激光是当前及今后固体可调谐激光领域的主要研究对象之一。该文综合评述了碱卤化物色心晶体及激光的研究发展概况，系统地探讨了色心的结构、光谱性质和色心晶体的制备，客观地分析了Ｆ型色心、Ｆ２＾＋型色心的发展、现状及主要激光性能。     

掺质KCl晶体F_A色心电子能级

在计算KCl晶体中的F_A心电子能级时,本文认为是基质和掺质对色心电子云束缚的松紧程度之差确定了电子云分布,据此对三种典型的掺质:Li:KCl:F_A(II);Cu:KCl:F_A(III);Ti:KCl:F_A(III),采用不同的出发点进行计算,结果和实验值比较,误差在5%以内.     

Tm：YAG晶体的光谱及激光特性研究

测试了Ｔｍ：ＹＡＧ晶体的室温吸收光谱和荧光光谱，计算了各吸收谱线的振子强度，并根据Ｊｕｄｄ－Ｏｆｅｌｔ理论了Ｔｍ：ＹＡＧ晶体的荧光跃迁截面和荧光寿命，用红宝石激光泵浦时，获得了波长２．０１μｍ能量４０ｍＪ的激光脉冲。     

LiF晶体中F3^＋—F2混合色心激光器

本文报道了室温下LiF晶体中F_3~+-F_2混合色心激光器.利用一块晶体和单一泵光,输出激光波长范围从510～580nm、640～710nm.总带宽140nm.     

飞秒脉冲激光对YAG晶体的辐照作用的研究

采用波长为800nm，脉冲宽度为120fs的飞秒激光对提拉法和温梯法生长的YAG晶体进行辐照。并对辐照后的样品进行吸收光谱及电子顺磁共振谱(EPR)的检测。结果表明，提拉法的晶体在经过辐照后，255nm吸收峰减弱，同时在370nm处产生新的宽峰吸收，其产生原因是由于样品内部分Fe^3 转化成Fe^2 ，并有少量F^ 心生成。对比两种不同方法生长的晶体，温梯法生长的YAG晶体的抗激光辐照能力略优于提拉法生长的晶体。     

Tm∶YAG晶体的光谱及激光特性研究

测试了Ｔｍ∶ＹＡＧ晶体的室温吸收光谱和荧光光谱，计算了各吸收谱线的振子强度，并根据Ｊｕｄｄ－Ｏｆｅｌｔ理论计算了Ｔｍ∶ＹＡＧ晶体的荧光跃迁截面和荧光寿命。用红宝石激光泵浦时，获得了波长２．０１μｍ、能量４０ｍＪ的激光脉冲。     

Yb：YAG晶体的制备与光谱特性

用引上法生长Ｙｂ：ＹＡＧ晶体，确定了合适的退火工艺，研究了Ｙｂ：ＹＡＧ晶体中Ｙｂ＾３＋的光谱性能双及晶体缺陷对Ｙｂ＾２＋光谱性能的影响。     

Variable temperature EPR spectra of Copper (II) ions in kainite crystals

X-band electron paramagnetic resonance (EPR) studies on divalent copper ions embedded in KMgClSO₄·3H₂O single crystals have been performed at low temperature (123 K). The angular variation of the EPR spectra reveals the presence of two Cu²⁺ sites, which have different orientations. The spin-Hamiltonian parameters of this six-coordinated cupric ion have been evaluated from the EPR spectra at 123 K. The forbidden lines due to Δm_I=±1 transitions are observed in between allowed transitions. The temperature variation EPR studies have also been performed both for a single crystal and a polycrystalline sample. The ground state wavefunction of Cu²⁺ ions has been estimated and is found to be an admixture of d_3z²−r² and d_x²−y². The temperature variation of the EPR spectra reveals that Cu²⁺ ions exhibit dynamic Jahn-Teller effect. From the polycrystalline EPR data, the temperature dependent magnetic susceptibilities are evaluated and discussed.     

Dielectric behavior,conduction and EPR active centres in BiVO4 nanoparticles

Bismuth vanadate (BiVO₄) nanomaterials were synthesized by mechano-chemical ball milling method and complementary investigations were devoted to their structures, nanoparticle morphologies and electronic active centres. The dielectric and conductivity behaviour were analysed systematically in wide temperature and frequency ranges to correlate such physical responses with the peculiarities of the samples. Large interfacial polarisations favoured by high specific surfaces of nanoparticles account for a drastic enhancement of the dielectric function in the quasi-static regime. Exhaustive analyses of the dielectric experiments were achieved and account for the main features of dielectric functions and their related relaxation mechanisms. The electrical conductivity is thermally activated with energies in the range 0.1–0.6 eV depending on the sample features. DC conductivity up to 10^–3 S/cm was obtained in well crystallized nanoparticles. Vanadium ions reduction was revealed by EPR spectroscopy with higher concentrations of the active centres (V⁴⁺) in more agglomerated and amorphous nanopowders. The EPR spectral parameters of V⁴⁺ were determined and correlated with the local environments of reduced vanadium ions and the characteristics of their electronic configurations. An insight is also made on the role of active electronic centres (V⁴⁺) on the conduction mechanism in nanostructured BiVO₄.     

EPR study of Cu(II) dopant ions in single crystals of bis(l-asparaginato)Zn(II)

We report an electron paramagnetic resonance (EPR) study at 33.9 GHz and room temperature of oriented single crystal samples of bis(l-asparaginato)Zn(II) doped with Cu(II). The variation of the spectra with magnetic field orientation was measured in three crystal planes (a*b, bc and a*c, with a*=b×c). These spectra display two groups of four peaks arising from the hyperfine interaction with the I_Cu=3/2 nuclear spins of copper. They were assigned to Cu(II) ions in two lattice sites related by a 180° rotation around the b-crystal axis. The g and hyperfine coupling (A) tensors of the Cu(II) ions were evaluated from the single crystal data. Some indeterminacy in the assignment of the signals was avoided measuring the EPR spectrum of a powder sample. Their principal values are g₁=2.060(1), g₂=2.068(2), g₃=2.283(2), and A₁≈0.1×10⁻⁴, A₂=13×10⁻⁴ and A₃=165×10⁻⁴ cm⁻¹. The eigenvectors corresponding to g₃ and A₃ are coincident within the experimental error; the other eigenvectors are rotated 5.6° in the perpendicular plane. Considering the crystal structure of bis(l-asparaginato)Zn(II), our EPR results indicate that the Cu(II) impurities replace Zn(II) ions in the host crystal. We propose a molecular model based on the EPR data and the structural information, and analyse the results comparing the measured values with those obtained in similar systems.     

Optical absorption, EPR, infrared and Raman spectral studies of clinochlore mineral

Optical absorption, EPR, Infrared and Raman spectral studies have been carried out on natural clinochlore mineral. The optical absorption spectrum exhibits bands characteristic of Fe²⁺ and Fe³⁺ ions. A band observed in the NIR region is attributed to an intervalence charge transfer (Fe²⁺-Fe³⁺) band. The room temperature EPR spectrum of single crystal of clinochlore mineral reveals the dominance of Fe³⁺ ion exhibiting resonance signals at g=2.66; 3.68 and 4.31 besides one isotropic resonance signal at g=2.0. The EPR studies have been carried out for a polycrystalline sample in the temperature range from 103 to 443 K and for a single crystal of clinochlore mineral in the temperature range 123-297 K. The number of spins (N) participating in resonance at g=4.3 signal of the single crystal of clinochlore mineral has been calculated at different temperatures. The paramagnetic susceptibility (χ) is calculated from the EPR data at different temperatures for single crystal of clinochlore mineral. The Curie constant and Curie temperature values are evaluated from 1/χ versus T graph. The infrared spectral studies reveal the formation of Fe³⁺-OH complexes due to the presence of higher amount of iron in this mineral. The Raman spectrum exhibits bands characteristic of Si-O-Si stretching and Si-O bending modes.     

Synthesis, X-ray structure, EPR and optical properties of a ferrocene substituted polychlorotriphenylmethyl radical

The optical, magnetic and electrochemical properties of the octamethylferrocene aldehyde substituted polychlorotriphenylmethyl radical 1 are reported. Radical 1 is prepared in a three step synthetic route starting with a Wittig-Horner reaction to yield (E)-1-formyl-1′-{2-{4-[bis(2,3,4,5,6-pentachlorophenyl)methyl]-2,3,5,6-tetrachloro phenyl}ethen-1-yl}-2,2′,3,3′,4,4′,5,5′-octamethyl ferrocene (6), which is subsequently deprotonated to yield the corresponding anion 7 and finally oxidized to (E)-4-[2-(1′-formyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocen)ethen-1-yl]-2,3,5,6-tetrachlorophenyl-bis(2,3,4,5,6-pentachlorophenyl)methyl radical (1). Radical 1 exhibits a charge-transfer band transition in the near infrared region which is associated with an intramolecular electron transfer from the ferrocene unit (donor) to the radical unit (acceptor) of this dyad molecule. The X-ray crystal structure of [K⁺(18-crown-6)] (E)-[4-[2-(1′-formyl-2,2′,3,3′,4,4′,5,5′-octamethylferrocen)ethen-1-yl]-2,3,5,6-tetrachlorophenyl-bis(2,3,4,5,6-pentachlorophenyl) methide] (7) has been determined. This organic salt shows an interesting one-dimensional polymeric structure formed by the coordination of the K⁺ cation with several atoms of the organic carbanion.     

EPR, luminescence and IR studies of Mn activated ZnGa2O4 phosphor

Electron paramagnetic resonance (EPR), luminescence and infrared spectra of Mn²⁺ ions doped in zinc gallate (ZnGa₂O₄) powder phosphor have been studied. The EPR spectra have been recorded for zinc gallate phosphor doped with different concentrations of Mn²⁺ ions. The EPR spectra exhibit characteristic spectrum of Mn²⁺ ions (S=I=5/2) with a sextet hyperfine pattern, centered at g_eff=2.00. At higher concentrations of Mn²⁺ ions, the intensity of the resonance signals decreases. The number of spins participating in the resonance has been measured as a function of temperature and the activation energy (E_a) is calculated. The EPR spectra of ZnGa₂O₄: Mn²⁺ have been recorded at various temperatures. From the EPR data, the paramagnetic susceptibility (χ) at various temperatures, the Curie constant (C) and the Curie temperature (θ) have been evaluated. The emission spectrum of ZnGa₂O₄: Mn²⁺ (0.08 mol%) exhibits two bands centered at 468 and 502 nm. The band observed at 502 nm is attributed to ⁴T₁→⁶A₁ transition of Mn²⁺ ions. The band observed at 468 nm is attributed to the trap-state transitions. The excitation spectrum exhibits two bands centered at 228 and 280 nm. The strong band at 228 nm is attributed to host-lattice absorption and the weak band at 280 nm is attributed to the charge-transfer absorption or d⁵→d⁴s transition band. The observed bands in the FT-IR spectrum are assigned to the stretching vibrations of M-O groups at octahedral and tetrahedral sites.     

A novel approach to the simulation of nitroxide spin label EPR spectra from a single truncated dynamical trajectory

A simple effective method for calculation of EPR spectra from a single truncated dynamical trajectory of spin probe orientations is reported. It is shown that an accurate simulation can be achieved from the small initial fraction of a dynamical trajectory until the point when the autocorrelation function of re-orientational motion of spin label has relaxed. This substantially reduces the amount of time for spectra simulation compared to previous approaches, which require multiple full length trajectories (normally of several microseconds) to achieve the desired resolution of EPR spectra. Our method is applicable to trajectories generated from both Brownian dynamics and molecular dynamics (MD) calculations. Simulations of EPR spectra from Brownian dynamical trajectories under a variety of motional conditions including bi-modal dynamics with different hopping rates between the modes are compared to those performed by conventional method. Since the relatively short timescales of spin label motions are realistically accessible by modern MD computational methods, our approach, for the first time, opens the prospect of the simulation of EPR spectra entirely from MD trajectories of real proteins structures.     

Synthesis, crystal structure, Cu doped EPR and voltammetric studies of bis[N-(2-hydroxyethyl)ethylenediamine]zinc(II) squarate monohydrate

Crystal structure of [Zn(hydet-en)₂]·C₄O₄·H₂O (ZHES) (hydet-en is N-(2-hydroxyethyl)ethylenediamine) complex has been synthesized and characterized by analytical, spectroscopic (IR, UV/Vis) and voltammetric techniques. After doping Cu²⁺ ion, its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystalizes in monoclinic system with space group P2₁/c and with Z=4. Each hydet-en ligand acts as a tridentate ligand through the two N atoms and the hydroxyl O atom, resulting in a six coordinate Zn(II) ion. The EPR spectra were recorded in three perpendicular planes of Cu²⁺ doped ZHES single crystal. The calculated g and A values indicated that the paramagnetic center is rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The molecular orbital bond coefficients of the Cu(II) ion in d⁹ state is also calculated by using EPR and optical absorption parameters. The dianion SQ²⁻ is oxidized reversibly in two consecutive steps to the corresponding radical monoanion and neutral form.     

Defects and impurities in nanodiamonds: EPR, NMR and TEM study

EPR, ¹³C NMR and TEM study of ultradisperse diamond (UDD) samples is reported. The compounds show a high concentration of paramagnetic centers (up to 10²⁰ spin/g), which are due to structural defects (dangling C-C bonds) on the diamond cluster surface. The anomalous reduction in the spin-lattice relaxation time of ¹³C (from several hours in natural diamond to ∼150 ms in UDD clusters) is attributed to the interaction between the unpaired electrons of the paramagnetic centers and nuclear spins. ¹³C NMR line-width reflects the fact that the structure of the UDD surface is distorted in comparison to the ‘bulk’ diamond structure.     

EPR and optical studies of Cu doped ammonium dihydrogen phosphate single crystals

Electron paramagnetic resonance (EPR) spectra of Cu²⁺ ion in ammonium dihydrogen phosphate are studied at liquid nitrogen temperature (77 K). Four magnetically inequivalent Cu²⁺ sites in the lattice are identified. The angular variation spectra of the crystal in the three orthogonal planes indicate that the paramagnetic impurity, Cu²⁺ enters the lattice substitutionally in place of NH₄⁺ ions. The spin Hamiltonian parameters are determined with the fitting of spectra to rhombic symmetry crystalline field. The ground state wave function of Cu²⁺ ion is constructed and found to be predominantly |x²-y²〉. The cubic field parameter (Dq) and tetragonal parameters (Ds and Dt) are determined from optical spectra at room temperature. By correlating EPR and optical absorption spectra, the bonding coefficients are calculated and nature of bonding of metal ion with different ligands in the crystal is discussed.