Photoacoustic spectroscopy study of neodymium complexes with alanine,valine, phenylalanine and tryptophan

Neodymium complexes with amino acids: Nd(Ala)(3)Cl(3).3H(2)O, Nd(Val)(3)Cl(3).3H(2)O, Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O (Ala: L-alanine, Val: L-valine, Phe: L-phenylalanine, Trp: L-tryptophan) are synthesized and their photoacoustic (PA) spectra are reported. The nephelauxetic ratio beta, bonding parameter b(1/2) and Sinha parameter delta are calculated based on their PA spectra. The variation of these parameters and correlation of them with the nature of metal-ligand bonding are discussed. The PA intensity analysis of the f-f transitions of neodymium ion is carried out by calculating the intensity branching vector. The environmental effect on the f-f transitions of neodymium ion is also studied. The branching vectors of the f-f transitions of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O are similar, which indicates the perturbation of the two ligand fields is similar. The branching vectors of energy levels 4G(5/2)+(2)G(7/2) of Nd(Phe)Cl(3).5H(2)O and Nd(Trp)(3)Cl(3).3H(2)O increase remarkably compared with those of Nd(Ala)(3)Cl(3).3H(2)O and Nd(Val)(3)Cl(3).3H(2)O. As the degree of covalency increases, the oscillator strength of the hypersensitive transition exhibits a corresponding increase. The relaxation process of Nd(Ala)(3)Cl(3).3H(2)O is established through its PA and electron absorption spectroscopy (EAS). A method used to resolve the PA amplitude spectrum is suggested. With the phase spectrum, PA absorption bands of Nd(Trp)(3)Cl(3).3H(2)O are resolved well in the region of ligand absorption.     

Near-infrared luminescent hybrid materials doped with lanthanide (Ln) complexes (Ln = Nd, Yb) and their possible laser application

The crystal structures of ternary Ln(DBM)(3)phen complexes (DBM = dibenzoylmethane, phen = 1,10-phenanthroline, and Ln = Nd, Yb) and their in situ syntheses via the sol-gel process are reported. The properties of the Ln(DBM)(3)phen complexes and their corresponding Ln(3+)/DBM/phen-co-doped luminescent hybrid gels obtained via an in situ method (Ln-D-P gel) have been studied. The results reveal that the lanthanide complexes are successfully in situ synthesized in the corresponding Ln-D-P gels. Both Ln(DBM)(3)phen complexes and Ln-D-P gels display sensitized near-infrared (NIR) luminescence upon excitation at the maximum absorption of the ligands, which contributes to the efficient energy transfer from the ligands to the Ln(3+) ions (Ln = Nd, Yb), an antenna effect. The radiative properties of the Nd(3+) ion in a Nd-D-P gel are discussed using Judd-Ofelt analysis, which indicates that the (4)F(3/2) --> (4)I(11/2) transition of the Nd(3+) ion in the Nd-D-P gel can be considered as a possible laser transition.     

Syntheses, structures, and spectroscopic properties of K9Nd[PS4]4, K3Nd[PS4]2, Cs3Nd[PS4]2, and K3Nd3[PS4]4

Four new quaternary alkali neodymium thiophosphates K 9Nd[PS 4] 4 ( 1), K 3Nd[PS 4] 2 ( 2), Cs 3Nd[PS 4] 2 ( 3), and K 3Nd 3[PS 4] 4 ( 4) were synthesized by reacting Nd with in situ formed fluxes of K 2S 3 or Cs 2S 3, P 2S 5 and S in appropriate molar ratios at 973 K. Their crystal structures are determined by single crystal X-ray diffraction. Crystal data: 1: space group C2/ c, a = 20.1894(16), b = 9.7679(5), c = 17.4930(15) A, beta = 115.66(1) degrees , and Z = 4; 2: space group P2 1/ c, a = 9.1799(7), b = 16.8797(12), c = 9.4828(7) A, beta = 90.20(1) degrees , and Z = 4; 3: space group P2 1/ n, a = 15.3641(13), b = 6.8865(4), c = 15.3902(13) A, beta = 99.19(1) degrees , and Z = 4; 4: space group C2/ c, a = 16.1496(14), b = 11.6357(7), c = 14.6784(11) A, beta = 90.40(1) degrees , and Z = 4. The structure of 1 is composed of one-dimensional (1) infinity{Nd[PS 4] 4} (9-) chains and charge balancing K (+) ions. Within the chains, eight-coordinated Nd (3+) ions, which are mixed with K (+) ions, are connected by [PS 4] (3-) tetrahedra. The crystal structures of 2 and 3 are characterized by anionic chains (1) infinity{Nd[PS 4] 2} (3-) being separated by K (+) or Cs (+) ions. Along each chain the Nd (3+) ions are bridged by [PS 4] (3-) anions. The difference between the structures of 2 and 3 is that in 2 the Nd (3+) ions are coordinated by four edge-sharing [PS 4] (3-) tetrahedra while in 3 each Nd (3+) ion is surrounded by one corner-sharing, one face-sharing, and two edge-sharing [PS 4] (3-) tetrahedra. The structure of 4 is a three-dimensional network with K (+) cations residing in tunnels running along [110] and [110]. The {Nd(1)S 8} polyhedra share common edges with four [PS 4] tetrahedra forming one-dimensional chains (1) infinity{Nd[PS 4] 2} (3-) running along [110] and [110]. The chains are linked by {Nd(2)S 8} polyhedra yielding the final three-dimensional network (3) infinity{Nd[PS 4] 2} (3-). The internal vibrations of both crystallographically independent [PS 4] (3-) anions of 2- 4 have been assigned in the range 200-650 cm (-1) by comparison of their corresponding far/mid infrared and Raman spectra (lambda exc = 488 nm) on account of locally imposed C 1 symmetry. In the Fourier-transform-Raman spectrum (lambda exc = 1064 nm) of 2- 4, very similar well-resolved electronic Raman (ER) transitions from the electronic Nd (3+) ground-state to two levels of the (4)I 9/2 ground manifold and to the six levels of the (4)I 11/2 manifold have been determined. Resonant Raman excitation via a B-term mechanism involving the (4)I 15/2 and (4)F 3/2 intermediate states may account for the significant intensity enhancement of the ER transitions with respect to the symmetric P-S stretching vibration nu 1. Broad absorptions in the UV/vis/NIR diffuse reflectance spectrum at 293 K in the range 5000-25000 cm (-1) of 2- 4 are attributed to spin-allowed excited quartet states [ (4)(I < F < S < G < D)] and spin-forbidden doublet states [ (2)(H < G < K < D < P)] of Nd (3+). A luminescense spectrum of 3 obtained at 15 K by excitation with 454.5 nm shows multiplets of narrow lines that reproduce the Nd (3+) absorptions. Sharp and intense luminescence lines are produced instead by excitation with 514.5 nm. Lines at 18681 ( (4)G 7/2), 16692 ( (4)G 5/2), 14489 ( (4)F 9/2), and 13186 cm (-1) ( (4)F 7/2) coincide with the corresponding absorptions. Hypersensitive (4)G 5/2 is split by 42 cm (-1). The most intense multiplet at about 16500 cm (-1) is assigned to the transition from (4)G 5/2 to the Stark levels of the ground manifold (4)I 9/2.     

Magnetic resonance investigation of vanadia and vanadium-molybdenum gels synthesized with peroxovanadate precursors

Vanadia gels and vanadium-molybdenum oxide gels were investigated using the magnetic resonance techniques, EPR spectroscopy and (51)V MAS NMR spectroscopy. The vanadium oxide gels were derived from the reaction of H(2)O(2) and V(2)O(5), and the vanadium-molybdenum oxide (VMoO) gels were derived from the reaction of peroxovanadates with an ammonium molybdate solution. EPR spectroscopy was utilized to determine quantitative information about the concentration of V(4+) paramagnetic species present in the samples and additional structural information about the V(4+) coordination environment. (51)V MAS NMR spectroscopy was used to elucidate the V(5+) electronic environment and how it changes as a function of molybdenum content. The observed line broadening of the (51)V NMR signal with increasing molybdenum content was correlated with an increase in the concentration of paramagnetic species as monitored by EPR spectroscopy. The evolution of various vanadium sites during thermal treatment was also investigated. This work provides further support for the hypothesis that the selectivity of VMoO catalysts in the oxidation of 1,3-butadiene to maleic anhydride is due to the presence of paramagnetic V(4+) sites.     

Fluorescence properties of Nd3+-doped tellurite glasses

The compositional and concentration dependence of luminescence of the (4)F(3/2)-->(4)I(J) (J=13/2, 11/2 and 9/2) transitions in four Nd(3+)-doped tellurite based glasses has been studied. The free-ion energy levels obtained for 60TeO(2)+39ZnO(2)+1.0Nd(2)O(3) (TZN10) glass have been analysed using the free-ion Hamiltonian model and compared with similar results obtained for Nd(3+):glass systems. The absorption spectrum of TZN10 glass has been analysed using the Judd-Ofelt theory. Relatively longer decay rates have been obtained for Nd(3+)-doped phosphotellurite glasses. The emission characteristics of the (4)F(3/2)-->(4)I(11/2) transition, of the Nd(3+):TZN10 glass, are found to be comparable to those obtained for Nd(3+):phosphate laser glasses. The non-exponential shape of the emission decay curves for the (4)F(3/2)-->(4)I(11/2) transition is attributed to the presence of energy transfer processes between the Nd(3+) ions.     

Photoluminescence and Raman studies of Sm3+ and Nd3+ ions in zirconia matrices: example of energy transfer and host-guest interactions

Photoluminescence and Raman studies on Sm(3+)- and Nd(3+)-doped zirconia are reported. The Raman studies indicate that the monoclinic (m) phase dominates up to a 10 at.% lanthanide level, while stabilization of the cubic phase is attained at approximately 20 and approximately 25 at.% of Sm(3+) and Nd(3+), respectively. Both systems are strongly luminescent under photo-excitation. The emission spectrum at 77 K of the ZrO(2):Sm(3+) system consists of a broad band at 505 nm, that corresponds to the zirconia matrix. At room temperature the band maximum blue-shifts to 490 nm. Sharper bands corresponding to f-f transitions within the Sm(3+)ion are also exhibited in the longer wavelength region of the spectrum. Exclusive excitation of the zirconia matrix provides sensitized emission from the acceptor Sm(3+) ion. The excitation profile is dominated by a broad band at 325 nm when monitored either at the zirconia or at one of the Sm(3+) emissions. A spectral overlap between the 6H(5/2)-->(4)G(7/2) absorption of the Sm(3+) ion with the zirconia emission leads to an efficient energy transfer process in the systems. Multiple facets of the spectral behavior of the Sm(3+) or Nd(3+) in the zirconia matrices, as well as the effects of compositions on the emission and Raman properties of the materials, and the role of defect centers in photoluminescence and the energy transfer processes are discussed.     

Uptake of cesium, strontium and europium by a poly(sodium acrylate-acrylic acid) hydrogel

The uptake of cesium, strontium and europium from dilute nitric acid solutions by a poly(sodium acrylate-acrylic acid) PAA hydrogel has been investigated. pH variations are consistent with cation exchange processes: COO(-), Na (+)H (+), COO(-), Na (+)M (m+) ( M (m+) = Cs (+)and Sr (2+)) and COOH Eu (3+). Saturation of the gel is achieved for metal/carboxylate ratios R = 0.5. The swelling ratios of gels loaded with metal cations are those of uncharged, shrunk gels (Sr, Eu) or of charged, swollen gels (Cs) in agreement with the formation of uncharged (COO)(2)Sr, (COO)(2)EuX (X = NO(3) or OH) type complexes and (COO(-), Cs(+)) ion pairs. The metal cations are extracted in the gels following the order of their affinities with carboxylic groups Eu(3+) > Sr(2+) > Cs(+). An increase of the ionic strength of the metal aqueous solution up to 0.5M NaNO(3) leads to slightly decrease the europium uptake by the PAA hydrogel, but 0.1M NaNO(3) is sufficient to prevent the Sr and Cs extractions.     

Effect of surface coverage on the conformation and mobility of C18-modified silica gels

C18-modified silica gels with surface coverages of 2 to 8.2 micromol m(-2), were prepared by different synthetic pathways and characterized by Fourier Transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance (NMR) spectroscopy, and chromatographic measurements. The effects of temperature and bonding density on the conformational order of C18-modified silica gels were studied in detail by FTIR spectroscopy. The silane functionality and degree of cross-linking of silane ligands on the silica surface were evaluated by 29Si cross-polarization magic-angle spinning (CP/MAS) NMR and the structural order and mobility of the alkyl chains were investigated by 13C CP/MAS NMR spectroscopy. CH2 symmetric and anti-symmetric stretching bands and CH2 wagging bands were used as IR probes to monitor the conformational order and flexibility of the alkyl chains in the C18 phases. Qualitative information about the conformational order was obtained from frequency shifts of the CH2 symmetric and anti-symmetric stretching bands. The relative amounts of kink/gauche-trans-gauche, double-gauche, and end-gauche conformers in the alkyl chains were determined by analysis of CH2 wagging bands. These results indicate that surface coverage plays a dominant role in the conformational order of C18-modified silica gels. The FTIR and NMR data are discussed in the context of the chromatographic shape-selectivity differences.     

Structural analysis and molecular modelling of the Cu/Zn-SOD from fungal strain Humicola lutea 103

The native form of Cu/Zn-superoxide dismutase, isolated from fungal strain Humicola lutea 103 is a homodimer that coordinates one Cu(2+) and one Zn(2+) per monomer. Cu(2+) and Zn(2+) ions play crucial roles in enzyme activity and structural stability, respectively. It was established that HLSOD shows high pH and temperature stability. Thermostability of the glycosylated enzyme Cu/Zn-SOD, isolated from fungal strain H. lutea 103, was determined by CD spectroscopy. Determination of reversibility toward thermal denaturation for HLSOD allowed several thermodynamic parameters to be calculated. In this communication we report the conditions under which reversible denaturation of HLSOD exists. The narrow range over which the system is reversible has been determined using the strongest test of two important thermodynamic independent variables (T and pH). Combining both these variables, the "phase diagram" was determined, as a result of which the real thermodynamic parameters (ΔC(p), ΔH(exp)°, and ΔG(exp)°) was established. Because very narrow pH-interval of transitions we assume they are as result of overlapping of two simple transitions. It was found that ΔH(o) is independent from pH with a value of 1.3 kcal/mol and 2.8 kcal/mol for the first and the second transition, respectively. ΔG(o) was pH-dependent in all studied pH-interval. This means that the transitions are entropically driven, these. Based on this, these processes can be described as hydrophobic rearrangement of the quaternary structure. It was also found that glycosylation does not influence the stability of the enzyme because the carbohydrate chain is exposed on the surface of the molecule.     

Study of lanthanide complexes with salicylic acid by photoacoustic and fluorescence spectroscopy

Solid complexes Ln(Sal)3.H2O (Sal: salicylic acid; Ln: La3+, Nd3+, Eu3+, Tb3+) are synthesized, and their photoacoustic (PA) spectra in the UV-Vis region have been recorded. PA intensities of central lanthanide ions are interpreted in terms of the probability of nonradiative transitions. It is found that PA intensity of the ligand increases in the order of Tb(Sal)3.H2O < La(Sal3).H2O < Eu(Sal)3.H2O < Nd(Sal)3.H2O. Different PA intensities of the ligand are interpreted by comparison with the fluorescence spectra. Ternary complexes Eu(Sal)3Phen and Tb(Sal)3Phen (Phen: 1,10-phenanthroline) are synthesized. Compared with their binary complexes, PA intensity of the ligand Sal decreases for Eu(Sal)3Phen, while the reverse is true for that of Tb(Sal)3Phen. The luminescence of Eu3+ increases remarkably when Phen is introduced, and luminescence of Tb3+ decreases greatly when Phen is added. The intramolecular energy transfer and relaxation processes in the complexes are discussed from two aspects: radiative and nonradiative relaxations.     

Preparation and optical properties of sol–gel materials doped with coumarin molecules

New optical materials containing coumarin (3-(3-(4-(dimethylamino)phenyl)propenoyl)-2H-chromen-2-one) in silica are reproducibly prepared by a sol–gel technique and characterized with UV/Vis and luminescence spectroscopy. The incorporation of the coumarin molecules in the silica gels is monitored with UV/Vis spectroscopy. The coumarin doped gels change their color with time which is attributed to a protonation of the dimethylamino group of the coumarin molecules during aging of the gels and is proved by UV/Vis spectroscopy. The process of protonation of the dimethylamino group is described as a second order reaction. The luminescence spectra of the coumarin doped gels at room temperature also are given.     

稀土三元配合物粉末和凝胶共发光效应的光声光谱研究

合成了Eu(TTA)3·Phen和Eu0.8Y0.2(TTA)3·Phen固体配合物微晶粉末及其掺杂的SiO2凝胶样品.在300～800nm测定并解释了其光声光谱.在配体吸收处,Eu0.8Y0.2(TTA)3@Phen的光声强度低于Eu(TTA)3@Phen的光声强度;而对于配合物掺杂的凝胶样品,则情况相反.Y3+的引入改变了配合物的弛豫过程,且配合物在粉末和凝胶状态下,弛豫历程不尽相同.结合荧光光谱研究了标题化合物的发光特性,并建立了能量传递模型.     

Optical characterization of Sm3+ and Dy3+:ZnO-PbO-B2O3 glasses

Here, we present the results of the analysis of Sm(3+) or Dy(3+) (0.5 mol%) ions doped heavy metal oxide (HMO)-based zinc lead borate (ZLB) glasses. Optical measurements such as absorption, emission spectra, lifetimes, XRD, DSC profiles have been carried out. The emission spectrum of Sm(3+):ZLB has shown the emission transitions of (4)G(5/2)-->(6)H(5/2) (563 nm), (4)G(5/2)-->(6)H(7/2) (598 nm), (4)G(5/2)-->(6)H(9/2) (646 nm), (4)G(5/2)-->(6)H(11/2) (708 nm) with lambda(exc): 401 nm ((6)H(5/2)-->(4)F(7/2)). In the case of the Dy(3+):ZLB glass, emission transitions of (4)F(9/2)-->(6)H(15/2) (485 nm), (4)F(9/2)-->(6)H(13/2) (575 nm) and (4)F(9/2)-->(6)H(11/2) (664 nm) with lambda(exi): 447 nm ((6)H(15/2)-->(4)I(15/2)) have been identified. Energy level schemes relating to the emission mechanisms involved in Sm(3+) and Dy(3+) glasses have been given.     

Selective Ion Pair Adsorption of Cobalt and Copper Salts on Cationically Produced Poly(1,3-divinylimidazolid-2-one)/Silica Hybrid Particles

For quantitative metal salt adsorption, poly(1,3-divinylimidazolid-2-one)/silica [poly BVU(cat.)/silica] particles with different polymer contents have been synthesized by a cationic surface polymerization of 1,3-divinylimidazolid-2-one onto silica. Preliminary experiments with the metal ion salts CoCl(2), CoI(2), CuCl(2), and FeCl(3) on poly-BVU(cat.)/silica particles, a radically produced poly-BVU(rad.) resin, and a cationically produced poly-BVU(cat.) resin have been carried in acetone solution to check the suitability of the adsorbents. The adsorption mechanism for Co(2+) and Cu(2+) on poly-BVU(cat.)/silica is in accordance with the Langmuir model for monolayer adsorption as shown by quantitative adsorption measurements by means of UV/vis spectroscopy. An ion pair adsorption mechanism is suggested for CoCl(2), CoI(2), and CuCl(2) on poly-BVU(cat.)/silica because both environments cationically produced poly-BVU and residual silanol groups are required for linking the cation and anion. ESR spectroscopic results of CoCl(2)-, CuCl(2)-, and FeCl(3)-poly-BVU(cat.)/silica hybrid adsorbates show selective adsorption for Co(2+) and Cu(2+). However, two different adsorption sites are indicated for Fe(3+) on poly-BVU(cat.)/silica. Copyright 2001 Academic Press.     

TDDFT investigation on nucleic acid bases: comparison with experiments and standard approach

A comprehensive theoretical study of electronic transitions of canonical nucleic acid bases, namely guanine, adenine, cytosine, uracil, and thymine, was performed. Ground state geometries were optimized at the MP2/6-311G(d,p) level. The nature of respective potential energy surfaces was determined using the harmonic vibrational frequency analysis. The MP2 optimized geometries were used to compute electronic vertical singlet transition energies at the time-dependent density functional theory (TDDFT) level using the B3LYP functional. The 6-311++G(d,p), 6-311(2+,2+)G(d,p), 6-311(3+,3+)G(df,pd), and 6-311(5+,5+)G(df,pd) basis sets were used for the transition energy calculations. Computed transition energies were found in good agreement with the corresponding experimental data. However, in higher transitions, the Rydberg contaminations were also obtained. The existence of pisigma* type Rydberg transition was found near the lowest singlet pipi* state of all bases, which may be responsible for the ultrafast deactivation process in nucleic acid bases.     

Double NASICON-type cell: ordered Nd3+ distribution in Li0.2Nd0.8/3Zr2(PO4)3

The NASICON compound Li(0.2)Nd(0.8/3)Zr(2)(PO(4))(3), synthesized by a sol-gel process, has been structurally characterized by TEM and powder diffraction (neutron and X-ray). It crystallizes in the space group R3[combining macron] (No. 148): at room temperature, the Nd(3+) ions present an ordered distribution in the [Zr(2)(PO(4))(3)](-) network which leads to a doubling of the classical c parameter (a = 8.7160(3) A, c = 46.105(1) A). Above 600 degrees C, Nd(3+) diffusion occurs leading at 1000 degrees C to the loss of the supercell. This reversible cationic diffusion in a preserved 3D [Zr(2)(PO(4))(3)](-) network is followed through thermal X-ray diffraction. Ionic conductivity measurements have been undertaken by impedance spectroscopy, while some results concerning the sintering of the NASICON compound are given.     

A new mechanism of Raman enhancement and its application

Strong electronic Raman bands corresponding to the transition between 4I9/2 and 4I11/2 manifolds of Nd3+, caused by a Raman-enhancement effect, are observed in the FT-Raman spectrum of Nd2O3. Neither resonance enhancement (RR) nor surface enhancement (SERS) accounts for the Raman enhancement observed here. We propose a new mechanism of Raman enhancement called the "feed-back" mechanism. A YAG laser excites the final state of the Raman transition (4I11/2 of Nd3+) to the 4F3/2 state and causes a significant decrease in the population of Nd3+ at the 4I11/2 state. This causes the population ratio of Nd3+ at 4I9/2 and 4I11/2 to deviate from the value required by Boltzmann's law. To restore equilibrium, Raman scattering is enhanced so that more Nd3+ ions are brought from the 4I9/2 state to the 4I11/2 state. This hypothesis gets support from the temperature-variable FT-Raman spectroscopic results. Additionally, obvious differences between the Stokes and anti-Stokes Raman spectrum of Nd3+ provide further evidence to support the feed-back mechanism. The Raman-enhancement effect confers on the electronic Raman bands a special ability to reflect the variation of coordinated structure around metal ions. The structural variations in polymer-metal ion composites and biomineralization systems have been investigated by using the electronic Raman bands.     

Silica-coated Ln3+-Doped LaF3 nanoparticles as robust down- and upconverting biolabels

The preparation of nearly monodisperse (40 nm), silica-coated LaF(3):Ln(3+) nanoparticles and their bioconjugation to FITC-avidin (FITC=fluorescein isothiocyanate) is described in this report. Doping of the LaF(3) core with selected luminescent Ln(3+) ions allows the particles to display a range of emission lines from the visible to the near-infrared region (lambda=450-1650 nm). First, the use of Tb(3+) and Eu(3+) ions resulted in green (lambda=541 nm) and red (lambda=591 and 612 nm) emissions, respectively, by energy downconversion processes. Second, the use of Nd(3+) gave emission lines at lambda=870, 1070 and 1350 nm and Er(3+) gave an emission line at lambda=1540 nm by energy downconversion processes. Additionally, the Er(3+) ions gave green and red emissions and Tm(3+) ions gave an emission at lambda=800 nm by upconversion processes when codoped with Yb(3+) (lambda(ex)=980 nm). Bioconjugation of avidin, which has a bound fluorophore (FITC) as the reporter, was carried out by means of surface modification of the silica particles with 3-aminopropyltrimethoxysilane, followed by reaction with the biotin-N-hydroxysuccinimide activated ester to form an amide bond, imparting biological activity to the particles. A 25-fold or better increase in the FITC signal relative to the non-biotinylated silica particles indicated that there is minimal nonspecific binding of FITC-avidin to the silica particles.     

Effect of fluorine ions on 2.7 μm emission in Er3+/Nd(3+)-codoped fluorotellurite glass

The 2.7 μm emission properties of Er(3+)/Nd(3+)-codoped fluorotellurite glasses were investigated in the present work. The thermal stability, refractive index, absorption and transmission spectra, and emission spectra were measured and investigated. The 2.7 μm emission in Er(3+)/Nd(3+)-codoped fluorotellurite glasses was enhanced with the increase of fluorine ions. The Judd-Ofelt analysis based on absorption spectra was performed in order to determine the Judd-Ofelt intensity parameters Ωt (t = 2, 4, 6), spontaneous emission probability, radiative lifetime and branching ratios of Er(3+):(4)I(11/2) → (4)I(13/2) transition. It is found that the Er(3+)/Nd(3+)-codoped fluorotellurite glass possesses a lower spontaneous transition probability A (58.95 s(-1)) but a higher branching ratio β (15.72%) corresponding to the stimulated emission of Er(3+):(4)I(11/2) → (4)I(13/2) transition. Additionally, the transmittance was also tested and reached a maximum when the molar concentration of ZnF(2) is 15%. The presence of fluorine ions greatly decreases the population of OH(-) groups, which affects the 2.7 μm emission effectively by means of decreasing the rate of energy transfer to impurities (e.g., OH(-) groups).     

Spectroscopic investigations of Nd3+ doped flouro- and chloro-borate glasses

Spectroscopic and physical properties of Nd(3+) doped sodium lead flouro- and chloro-borate glasses of the type 20NaX-30PbO-49.5B(2)O(3)-0.5Nd(2)O(3) (X=F and Cl) have been investigated. Optical absorption spectra have been used to determine the Slater Condon (F(2), F(4), and F(6)), spin orbit xi(4f) and Racah parameters (E(1), E(2), and E(3)). The oscillator strengths and the intensity parameters Omega(2), Omega(4) and Omega(6) have been determined by the Judd-Ofelt theory, which in turn provide the radiative transition probability (A), total transition probability (A(T)), radiative lifetime (tau(R)) and branching ratio (beta) for the fluorescent level (4)F(3/2). The lasing efficiency of the prepared glasses has been characterized by the spectroscopic quality factor (Omega(4)/Omega(6)), the value of which is in the range of 0.2-1.5, typical for Nd(3+) in different laser hosts. Nephelauxetic effect results in a red shift in the energy levels of Nd(3+) for chloroborate glass. The radiative transition probability of the potential lasing transition (4)F(3/2)-->(4)I(11/2) of Nd(3+) ions is found to be higher for flouroborate as compared to chloroborate glass.