E.S.R. Spectra of the Cyclobutanesemidiones Derived from Three Tricyclo[4. 4. 2. 01,6,]Dodecane-11-OL-12-Ones

The semidione radical anions derived from a variety of alicyclic ketones and α-hydroxyketones have been extensively investigated via esr by Russell and co-workers.¹Studies of the chemistry and spectra of the 1, 2-cyclobutanediones derived from the tricyclo[4. 4. 2. 0^1,6] dodecane-11-o1-12-one system²suggested that an examination of the esr spectra of the related semidiones would be of considerable interest. The recent reports on the esr spectra of cyclobutanes emidione^1cand several substituted cyclo-butanes emidiones^1bfurther prompt this communication.     

Spectroscopic characterization of a Tm3+:SrGdGa3O7 crystal

3 O₇ crystal have been recorded at room temperature and at approximately 8 K. Room-temperature luminescence lifetimes of ¹D₂, ¹G₄, ³H₄, and ³F₄ states have been measured for Tm concentration ranging from [%at.]0.5 to [%at.]9. Based upon these data the crystal field splitting of luminescent states has been derived and radiative transitions rates have been evaluated. Strong self-quenching of luminescence originating in the ¹G₄ and ³H₄ states has been found in this activator–host combination. Peak emission cross section of the potential laser transition at 1800 nm was determined to be 3.9×10^-21 cm² and the gain coefficient versus wavelength was estimated and discussed. Received: 14 April 1998/Revised version: 10 August 1998     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998     

Modeling of recognition sites of nucleic acid bases aaand amide side chains of amino acids. Combination of experimental and theoretical approaches

A combined experimental-theoretical approach to modeling of building blocks of recognition complexes formed by nucleic acid bases and the amino-acids side-chain amino group is reviewed. The approach includes the temperature dependent field-ionization mass spectrometry and ab initio quantum chemical calculations. The mass spectrometric technique allows determination of interaction enthalpies of biomolecules in the gas phase, and the results it produces are directly comparable to the results obtained through theoretical modeling. In our works we have analyzed both thermodynamic and structural aspects of the recognition complexes of four canonical nucleic acid bases and acrylamide, which models the side chain of asparagine and glutamine. It has been shown that all bases can interact with amide group of the amino acids via their Watson-Crick sites when being incorporated into a single strand DNA or RNA. Stability of the complexes studied, expressed as - ΔH (kJ mole^-1) decreases as: m⁹Gua (- 59.5) > m ¹Cyt (- 57.0) > m ⁹Ade (- 52.0) ≫m ¹Ura (- 40.6). We have determined that in the double stranded DNA only purine bases can be recognized. Received 5 February 2002 and Received in final form 14 March 2002 Published online 13 September 2002     

Fourier spectroscopy of the OD infrared spectrum. Merge of electronic,vibration-rotation,and microwave spectroscopic data

The OD infrared spectrum, emitted in a flame of deuterium and oxygen, has been recorded for the first time in the 2-μm spectral range with a Fourier Transform spectrometer. A simultaneous fit of the ir 2-0, 3-1, 4-2, 5-3, 3-0, 4-1 vibration-rotation bands, of the uv data (0-0, 1-1, 2-2, 0–1 bands of the A²Σ⁺ → X²Π transition) and of the microwave data, gives accurate molecular constants for the ground-state vibrational levels up to v = 5. The classical “unique perturber approach” and the effective Hamiltonian of Brown for ²Π states, have been successively used for the reduction of the spectroscopic data.     

Electrochemiluminescence of Solution Mixtures I. Anthantrene, 9,10-Diphenylanthracene,Rubicene, Rubrene

Since the original paper by Hercules¹describing the electrogenerated chemiluminescence (ECL) of aromatic hydrocarbons in aprotic solvents, several publications^2-9 have dealt with the mechanisms of the phenomenon. Some work has also been concerned with possible analytical applications and concentration-intensity relationships have been discussed^11-13.     

N.M.R. investigation of critical orientational order fluctuations below the nematic-isotropic transition in liquid crystals

The high-resolution infra-red spectrum of SiH₄ in the region 2101 cm^-1 to 2265 cm^-1 has been analysed. Most of the lines observed have been assigned to transitions of the v ₃ and v ₁ bands of the abundant isotopic species ²⁸SiH₄. The v ₁ band is formally forbidden in the infra-red, but a vibration-rotation interaction between v ₁ and v ₃ lends intensity to the v ₁ transitions. The spectrum has been fitted by diagonalizing the v ₃ = 1 and v ₁ = 1 hamiltonians coupled by the vibration-rotation interaction term. 500 transitions have been fitted with an overall standard deviation of 0·007 cm^-1, using only 15 adjustable parameters (ten in the v ₃ = 1 hamiltonian, four in the v ₁ = 1 hamiltonian, and one interaction coefficient). The calculated intensities are also in good agreement with experiment. Transitions of the other isotopic species ²⁹SiH₄ and ³⁰SiH₄ have also been observed, but these spectra have not been analysed in detail.     

Spectroscopic properties and exicted-state relaxation dynamics of Er3+ in LiNbO3

Nonequivalent Er³⁺ sites in LiNbO₃ crystals have been evidenced by low-temperature optical absorption measurements. The radiative transition rates for the ⁴ S _3/2, ⁴ F _9/2, ⁴ I _9/2, ⁴ I _11/2, and ⁴ I _13/2 levels have been evaluated by the Judd-Ofelt method, and the contribution of multiphonon relaxation to the decay of excited states has been estimated. The quantum efficiency of the ⁴ I _11/2 level has been estimated to be 6% only, thus the excitation of levels lower than ⁴ S _3/2 is expected to populate efficiently the ⁴ I _13/2 level.     

Optical properties of Er/Yb-codoped transparent PLZT ceramic

Optical absorption and emission spectra of Er³⁺/Yb³⁺ ions in PLZT (Pb_1−xLa_xZr_yTi_1−yO₃) ceramic have been studied. Based on the Judd—Ofelt (J-O) theory, the J-O intensity parameters were calculated to be Ω₂=2.021×10⁻²⁰ cm², Ω₄=0.423×10⁻²⁰ cm², Ω₆=0.051×10⁻²⁰ cm² from the absorption spectrum of Er³⁺/Yb³⁺-codoped PLZT. The J-O intensity parameters have been used to calculate the radiative lifetimes and the branching ratios for some excited ⁴I_13/2, ⁴I_11/2, ⁴I_9/2⁴F_9/2, and ⁴S_3/2 levels of Er³⁺ ion. The stimulated emission cross-section (8.24×10⁻²¹ cm²) was evaluated for the ⁴I_13/2→⁴I_15/2 transition of Er³⁺. The upconversion emissions at 538, 564, and 666 nm have been observed in Er³⁺/Yb³⁺-codoped PLZT by exciting at 980 nm, and their origins were identified and analyzed.     

Infrared-to-red upconversion luminescence in samarium-doped antimony glasses

A new antimony-based glass system (K₂O-B₂O₃-Sb₂O₃) having low phonon energy (about 600 cm⁻¹) doped with Sm³⁺ ions has been developed. Infrared reflection spectroscopic (IRRS) studies have been employed to establish its low phonon energy. Ultraviolet-Visible-near infrared (UV-Vis-NIR) absorption and photoluminescence upconversion properties with the spectrochemistry of the 15K₂O-15B₂O₃-70Sb₂O₃ (mol%) glasses have been studied doping with different concentrations (0.1-1.0 wt%) of Sm₂O₃. UV-Vis-NIR absorption band positions have been justified with quantitative calculation of nephelauxetic parameter and covalent bonding characteristics of the host. NIR to visible upconversion has been investigated by exciting at 949 nm at room temperature. Three upconverted bands originating from the ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2 and ⁴G_5/2→⁶H_9/2 transitions are found to be centered at 566 (green, weak), 602 (orange, weak) and 636 (red, remarkably strong) nm, respectively. These bands have been explained from the evaluation of the absorption, normal (downconversion) fluorescence and excitation spectra. The upconversion processes have been explained by the excited state absorption (ESA), energy transfer (ET) and cross-relaxation (CR) mechanisms involving population of the metastable (storage) energy level (⁴G_5/2) by multiphonon deexcitation effect. It is evident from the IRRS study that the upconversion phenomena are expedited by the low multiphonon relaxation rate in antimony glasses owing to their low phonon energy (602 cm⁻¹, the main and highest intensity Sb-O-Sb stretching band) which is very close to that of fluoride glasses (500-600 cm⁻¹).     

Measurements of photoionization cross sections from the 4p, 5d and 7s excited states of potassium

New measurements of the photoionization cross sections from the 4p ²P_1/2,3/2, 5d ²D_5/2,3/2 and 7s ²S_1/2 excited states of potassium are presented. The cross sections have been measured by two-step excitation and ionization using a Nd:YAG laser in conjunction with a thermionic diode ion detector. By applying the saturation technique, the absolute values of the cross sections from the 4p ²P_3/2 and 4p ²P_1/2 states at 355 nm are determined as 7.2±1.1 and 5.6±0.8 Mb, respectively. The photoionization cross section from the 5d ²D_5/2,3/2 excited state has been measured using two excitation paths, two-step excitation and two-photon excitation from the ground state. The measured values of the cross sections from the 5d ²D_5/2 state by two-photon excitation from the ground state is 28.9±4.3 Mb, whereas in the two-step excitation, the cross section from the 5d ²D_3/2 state via the 4p ²P_1/2 state and from the 5d ²D_5/2,3/2 states via the 4p ²P_3/2 state are determined as 25.1±3.8 and 30.2±4.5 Mb, respectively. Besides, we have measured the photoionization cross sections from the 7s ²S_1/2 excited state using the two-photon excitation from the ground state as 0.61±0.09 Mb.     

Role of Yb and Tm ions in upconversion emission of Tb under 798 and 980 nm laser excitations in Tb-Tm-Yb doped tellurite glass

Upconversion emission and energy transfer processes in singly, doubly and triply doped tellurite glasses have been studied under 798 and 980 nm laser excitations. Emissions have been observed at 482, 544, 584, 655 nm and at 477, 655, 698, 800 nm corresponding to Tb³⁺: ⁵D₄ → ⁷F₆, ⁷F₅, ⁷F₄, ⁷F_J (J = 0, 1, 2, 3) and Tm³⁺: ¹G₄ → ³H₆, ¹G₄ → ³F₄, ³F₃ → ³H₆, ³H₄ → ³H₆ transitions, respectively. Among Tm³⁺, Yb³⁺and Tb³⁺ ions only Tm³⁺ has a ground state absorption at 798 nm excitation due to ³H₄ ← ³H₆ transition. For 980 nm excitation only Yb³⁺ can absorb the incident radiation. However, for both types of excitations, emission from all the three ions Tb, Yb and Tm has been observed. Possible mechanisms are proposed as follows: under 798 nm excitation Tm³⁺ ions are excited which excite Yb³⁺ ions through energy transfer. Finally “cooperative energy transfer” from a pair of Yb³⁺ ions to Tm³⁺ and Tb³⁺ ions takes place. Under 980 nm excitation Yb³⁺ ions absorb the incident energy and excite Tm³⁺ and Tb³⁺ ions via cooperative energy transfer. Variation of emission intensity with the ion concentrations of Yb³⁺, Tm³⁺ and Tb³⁺ has been studied. The lifetime of the ¹G₄ level has also been measured.     

Two-color three-photon resonant excitation spectrum of strontium in the autoionization region

We report new studies of the odd parity autoionizing Rydberg series of strontium attached to the 4d( ² D _{3/2, 5/2}) ionic limits possessing J = 1-3 based on the two-color three photon resonant excitation technique in conjunction with an atomic beam apparatus. Using the 4d ²³ P ₀ intermediate levels, we have been able to record the autoionizing Rydberg series of J = 1 whereas, from the 4d ²³ P ₂ intermediate level the series of Rydberg levels possessing J = 1, 2 and 3 have been observed. The level assignments and the line shapes simulations of the autoionizing resonances have been made using the multichannel quantum defect theory. Received 21 November 2001 / Received in final form 2 May 2002 Published online 19 July 2002     

Far infrared measurements of (TMTSF)2ClO4

Polarized far infrared reflectance measurements from 20 to 330 cm^?1 have been made on the organic superconductor (TMTSF)₂ClO₄. The feature in the reflectance at 28 cm^?1 has been studied as a function of temperature and applied magnetic field. Our results suggest that this feature is associated with a coupled electron-phonon mode rather than a pseudogap due to fluctuational superconductivity as has been suggested by others. In addition, a Kramers-Kronig analysis of the reflectance indicates that there is a concentration of oscillator strength above 100–150 cm^?1.     

Radiative lifetimes of Zn I highly excited states

The energy levels and lifetimes of 4sns³S₁ (n=5-25), 4snd³D₁ (n=4-25) and 4snp¹P₁ (n=5-15) of Zn I have been evaluated using the multichannel quantum defect theory (MQDT). The calculated lifetimes of 4sns³S₁ and 4snd³D₁ characterized by the effective quantum ν are given by the formula and , respectively.     

Luminescence spectroscopy of Er-doped and Er, Yb-codoped LaPO4 single crystals

LaPO₄ single crystals lightly doped with Er³⁺, and codoped with Er³⁺ and Yb³⁺ have been grown by spontaneous nucleation in a lead phosphate flux. Absorption and luminescence spectra have been measured in the visible and near-IR regions and the excited state dynamics has been studied upon pulsed laser excitation. The obtained results have allowed the evaluation of the effective emission cross-sections around 1.5 μm, that have been found to be similar to important oxide laser crystals doped with Er³⁺. Efficient visible upconversion has been observed upon excitation at 980 nm in the codoped crystals. This behaviour is attributed to Yb³⁺-Er³⁺ energy transfer processes.     

Spectral-kinetic characteristics of Pr luminescence in LiLuF4 host upon excitation in the UV-VUV range

Spectral-kinetic study of Pr³⁺ luminescence has been performed for LiLuF₄:Pr(0.1 mol%) single crystal upon the excitation within 5-12 eV range at T=8 K. The fine-structure of Pr³⁺ 4f ²→4f 5d excitation spectra is shown for LiLuF₄:Pr(0.1 mol%) to be affected by the efficient absorption transitions of Pr³⁺ ions into 4f 5d involving 4f ¹ core in the ground state. Favourable conditions have been revealed in LiLuF₄:Pr(0.1 mol%) for the transformation of UV-VUV excitation quanta into the visible range. Lightly doped LiLuF₄:Pr crystals are considered as the promising luminescent materials possessing the efficient Pr³⁺³P₀ visible emission upon UV-VUV excitation. The mechanism of energy transfer between Lu³⁺ host ion and Pr³⁺ impurity is discussed.     

Thermodynamic studies of successive phase transitions in BaZnGeO4 and a new solid phase below 186.1 K

The successive phase transitions of BaZnGeO₄ have been studied on meltsolidified samples. A new solid phase (named phase VI) has been found below 186.1 K in samples of large particle size (diameter:D0.1 mm). The higher temperature crystalline phase V can be supercooled easily down to liquid helium temperature. On heating, however, it transforms into phase VI above 95 K in a slow exothermic process. Heat capacities have been measured by adiabatic calorimetry between 14 and 300 K. The enthalpy and entropy of the V–VI phase transition are 187.1 Jmol^–1 and 0.971 J K^–1 mol^–1, respectively. The corresponding data for the IV–V phase transition at 199.8 K are 229.3 J mol^–1 and 1.168 JK^–1 mol^–1. The phase VI does not appear in samples of smaller particle size (D0.1 mm).     

The association of octadecyl-end-capped poly-(sodium 2-acrylamido-2-methylpropanesulfonates) in water and salt solutions: A study by fluorescence spectroscopy and isothermal titration calorimetry

Steady-state fluorescence spectroscopy and isothermal titration calorimetry (ITC) have been used to study the aggregation in aqueous solutions of poly-(2-acrylamido)-2-methylpropanesulfonic acids, sodium salt mono-endcapped with either N,N-di-n-octadecyl or N-4-[(1-pyrenyl)butyl]-N-n-octadecyl which were prepared by free radical polymerization of 2-(acrylamido)-2-methylpropane sulfonic acid (AMPS) initiated with the azo compounds, 4,4'-azobis{cyano-N,N-di-n-octadecyl}pentanamide and 4,4'-azobis{cyano-N,N-[4-(1-pyrenyl)butyl]-n-octadecyl}pentanamide, respectively. Both techniques indicate the occurrence of multimolecular aggregates in solutions of the polymers in water and in 0.2 M NaCl. The concentration range for aggregation is about 1-14 mmol AMPS l^-1 (0.5-2.7 g l^-1) in 0.2 M NaCl and the enthalpy of micellization, estimated from ITC data, is ∼100 J [mol AMPS]^-1. The accessibility of the chromophores to neutral molecules and to cationic species was assessed by quenching of fluorescence with nitromethane and thallium nitrate, respectively. The association of the mono-endcapped polymers is compared to that of PAMPS derivatives carrying hydrophobic groups randomly attached along the chain. Received 7 August 2000 and Received in final form 26 October 2000     

Gamma-ray spectroscopy of the neutron-rich Ni region through heavy-ion deep-inelastic collisions

Nuclei in the neutron-rich Ni region have been studied by γ-ray spectroscopy. Gamma-rays emitted from isomers, with T _1/2 > 1 ns, produced in heavy-ion deep-inelastic collisions were measured with an isomer-scope. The nuclear structure of the doubly magic ⁶⁸Ni and its neighbor ^69,71Cu is discussed on the basis of the shell model. Future experiments for more neutron-rich Ni nuclei are also viewed. Received: 1 May 2001 / Accepted: 4 December 2001