ORNL developments in laser ion sources for radioactive ion beam production

The development of a resonant ionization laser ion source (RILIS) for the production of isotopically pure radioactive ion beams is reported. The application of the laser ion source calls for high elemental selectivity, high efficiency, and fast release of short-lived isotopes. A hot-cavity ion source and three Ti:sapphire lasers pulsed at a 10 kHz rate are employed for the RILIS. The Ti:sapphire lasers have been upgraded with individual pump lasers to eliminate intracavity Pockels cells and output losses due to synchronization delays. The development of ionization schemes for a wide range of elements is important to the success of Ti:sapphire-laser-based RILIS. In off-line studies with stable isotopes, resonant ionization of 14 elements has been studied, leading to new ionization schemes for ten elements. The absolute ionization efficiency of the hot-cavity RILIS has been measured to range from 0.9 % to 40 % for different elements. The mechanisms for ion transportation and confinement in the hot-cavity ion source have been studied using the temporal profiles of the laser-ionized ions. The hot-cavity RILIS has provided beams of neutron-rich $^{83,85,86}$ Ga isotopes for beta decay studies and enabled the first measurement of the beta decay of the exotic $^{86}$ Ga.     

Laser assisted decay spectroscopy at the CRIS beam line at ISOLDE

The new collinear resonant ionization spectroscopy (Cris) experiment at Isolde, Cern uses laser radiation to stepwise excite and ionize an atomic beam for the purpose of ultra-sensitive detection of rare isotopes and hyperfine structure measurements. The technique also offers the ability to purify an ion beam that is contaminated with radioactive isobars, including the ground state of an isotope from its isomer. A new program using the Cris technique to select only nuclear isomeric states for decay spectroscopy commenced last year. The isomeric ion beam is selected using a resonance within its hyperfine structure and subsequently deflected to a decay spectroscopy station. This consists of a rotating wheel implantation system for alpha and beta decay spectroscopy, and up to three high purity germanium detectors for gamma-ray detection. This paper gives an introduction to the Cris technique, the current status of the laser assisted decay spectroscopy set-up and recent results from the experiment in November 2011.     

Synthesis and EPR spectroscopy of nitroxyl derivatives of the C60 fullerene

The 2,2,5,5-tetramethyl-3-imidazoline-3-oxy-1-oxyl-4-(azidophenyl) derivatives of the C₆₀ fullerene with one (compound I), two (compound II), and three (compound III) nitroxyl groups are synthesized and studied by EPR spectroscopy. It is demonstrated that successive addition of nitroxyl radicals to C₆₀ leads to a decrease in the rotational mobility of molecules. Chromatographically inseparable isomers are found for compounds II and III.     

EPR,the X-ray Structure and DFT Calculations of the Nitroxide Biradical with One Acetylene Group in the Bridge

Two short nitroxide biradicals of similar composition, R6′–R6′ (B0) and R6′–(C ≡ C)–R6′ (B1), where R6′ is 1-oxyl-2,2,6,6-tetramethyl-3,4-ene-nitroxide ring, have been investigated by electron paramagnetic resonance spectroscopy and X-ray structural analysis. Quantum chemical calculations at UDFT/B3LYP/cc-pVDZ level were also performed and compared with the X-ray structural data. Zero-field splitting parameters D for B0 and B1 were found to be equal ?0.0048 and ?0.0022 cm^?1, respectively, in good agreement with quantum chemical prediction. Potential energy surface scans corresponding to pathways of the conformational rearrangements were calculated; rotation barriers for B0 and B1 were found to be 19.2 and 4.0 kJ/mol, respectively; and structural rigidity and probable differences in biradicals behavior are discussed. Calculations of spin density distribution in biradicals B0 and B1 were also carried out.     

Dual-wavelength diode-pumped laser operation of N p-cut and N g-cut Tm:KLu(WO4)2 crystals

Simultaneous continuous-wave laser oscillation at two wavelengths has been observed and studied in a diode-pumped monoclinic N _p-cut Tm:KLu(WO₄)₂ for different transmission of the output coupler. The maximum output power reached 1.15 W with a slope efficiency of 20.4 % with respect to the absorbed power for polarization parallel to the N _m optical axis. In an analogous N _g-cut crystal, the dual-wavelength laser operation is accompanied by polarization switching with increasing pump power and the switching point depends on the output coupling. The thresholds are slightly higher, and the slope efficiency reached a maximum of 25.5 % for polarization parallel to N _m at low pump levels, but at high pump levels, the oscillating polarization is parallel to N _p, reaching maximum output power of 3.09 W. Simple modelling with rate equations taking into account reabsorption losses explains qualitatively the complex behavior observed in the continuous-wave laser experiments with this anisotropic biaxial laser crystal.     

Structure, phase (aggregate) state, and optical properties of a new heat-resistant polymer with a nonlinear optical chromophore

A new heat-resistant copolymer (II) with a nonlinear optical chromophore in a side chain was synthesized by the etherification of side hydroxyl groups in chains of silicon-containing poly(o-hydroxyamide) (I) with 4′-{(6-chlorohexyl)methylamino}-4-nitroazobenzene (chromophore) under conditions of phase-transfer catalysis. The structure and phase (aggregate) states of copolymer II were investigated using x-ray diffraction and differential scanning calorimetry. It was shown that the substitution of chromophore molecules for up to 15% of hydrogen atoms in hydroxyl groups of amorphous copolymer I most likely leads to an independent arrangement of the chromophoric groups and the formation of crystal domains. It was established that this ordering substantially affects the stability and efficiency of the nonlinear optical properties of films prepared from copolymer II and is probably responsible for the slow decay of the second-harmonic generation signal in the sample.     

Optical gain analysis of strain-compensated InGaN–AlGaN quantum well active regions for lasers emitting at 420–500 nm

Strain-compensated InGaN quantum wells with tensile AlGaN barriers are analyzed as improved gain media for laser diodes emitting at 420–500 nm. The band structure is calculated using the 6-band k ·p formalism, taking into account valence band mixing, strain effect, and spontaneous and piezoelectric polarizations. The optical gain analysis exhibits significant improvement in the peak optical gain and differential gain for the strain-compensated structures. The calculation also shows a significant reduction of threshold carrier density and current density for diode lasers employing the strain-compensated InGaN–AlGaN QW active regions.     

Synchronization between optically injected semiconductor lasers on undamped relaxation oscillations

Seeding light from a laser into the cavity of a second one is a simple experiment largely encountered in optical domain (Stover, H.L., Steier, W.H.: Appl. Phys. Lett. 8, 91–93 (1966); Lang, R.: IEEE J. Quant. Elect. 18(6), 976–983 (1982)). With an unidirectional coupling, optical injection is a basic tool to study synchronization process between oscillators. The dynamics induced in this experiment have been extensively described, theoretically and experimentally (Simpson, T.B. et al.: Quant. Semiclassical Opt. 9(5), 765–784 (1997); Wieczorek S.: Opt. Commun. 172, 279–295 (1999); Blin, S.: Comptes Rendus de la Phys. 4(6), 687–699 (2003)) but mainly when the seeded light is a continuous wave (CW). In this paper, we describe the synchronization on an undamped relaxation regime. In order to study the degree of correlation between the two synchronized lasers (TL and RL), we use a cascade of two optical injections (Guignard, C.: Conference on Lasers and Electro Optics—the Europeen Quant. Electronics Conference (CLEO-EQEC), Munich (Germany), EC1M (2003)) thus three lasers: Master-transmitter laser (TL)-receiver laser (RL). The seeding by a field showing undamped relaxations can be directly compared with the optical injection by a CW signal, especially when the injected power and the detuning between the TL and RL frequencies are varied. Synchronization on undamped relaxation are shown to occur at values of the optical injected power and detuning, for which the RL is in the locked or wave-mixing regime when it is seeded by a CW. However, additional tongues of synchronization also exist at detuning equal to the relaxation oscillation frequency (ROF).     

The Reaction of Synechocystis Catalase–Peroxidase (KatG) with Isoniazid Investigated by Multifrequency (9–285 GHz) EPR Spectroscopy

Three distinct electron paramagnetic resonance (EPR) spectra of radical intermediates formed as reactive intermediates in the catalytic cycle of Synechocystis catalase–peroxidase were identified. Multifrequency EPR spectroscopy, combined with site-directed mutagenesis and selective deuterium labeling of Trp and Tyr residues, allowed us to unequivocally assign such intermediates to an [Fe(IV) = O Por ^·+] species, the first committed intermediate in monofunctional peroxidases and two protein-based radicals, identified as Trp106 ^· and a Tyr ^· , formed subsequently to the [Fe(IV) = O Por ^·+] species by intramolecular electron transfer. Our recent characterization of the Mycobacterium tuberculosis catalase–peroxidase showed that the Trp ^· sites differ among these enzymes, and that the [Fe(IV) = O Trp ^· ] species was the reactive intermediate with the prodrug isoniazid. Accordingly, the question to address was whether the dissimilarity in the sites for the formation of the Trp ^· intermediates and in the geometry of the distal side was reflected by differences in the peroxidase-like reaction of Synechocystis and Mycobacterium tuberculosis catalase–peroxidases with the prodrug isoniazid. Our findings show that in the Synechocystis enzyme, the isoniazid substrate can get closer to the heme distal side and can react readily with the [Fe(IV) = O Por ^·+] species, at variance to the situation in the M. tuberculosis catalase–peroxidase. These results indicate that, as in the case of monofunctional peroxidases, the difference in the sites for the formation of the Trp ^· as alternative reactive intermediates to the [Fe(IV) = O Por ^·+] species is correlated to differences in substrate binding sites.     

Nitrogen optical emission during nanosecond laser ablation of metals: prompt electrons or photo-ionization?

Experiments on the interaction of metal targets with a Nd:YAG laser beam ( \(\lambda \)  = 1,064 nm, intensity \(10^{10}\) – \(10^{11}\,\hbox {W/cm}{^2}\) ) are carried out in a finite Nitrogen pressure environment. The observed \(\hbox {N}_2\) spectra are unambiguous evidence of the existence of an ionization and excitation source, arriving at the observation volume prior to the plume. Such a source can be either prompt electrons or VUV radiation. The analysis reveals that the prompt electron interpretation requires energies in excess of 1 keV, incompatible with any acceleration mechanisms relevant for such laser intensities. On the other hand, VUV radiation is sufficiently strong to explain the observed spectra.     

Coordination preference and magnetic properties of FeII assemblies with a bis-azole bearing 1,2,4-triazole and tetrazole

With a new bis-azole molecular fragment (Htt) bearing 1,2,4-triazole and tetrazole, a mononuclear complex [Fe(tt)₂(H₂O)₄]·2H₂O (1), a trinuclear complex [Fe₃(tt)₆(H₂O)₆]·2H₂O (2) and a 1D coordination polymer [Fe(tt)(Htt)₂]BF₄·2CH₃OH (3) were obtained by varying reaction conditions. Htt acts either as an anionic or neutral ligand depending upon the reaction medium and pH. Thermal variation of spin states of 1–3 were investigated in the range 77–300?K by ⁵⁷Fe M?ssbauer spectroscopy. 1 totally remains in high-spin state over the entire temperature range whereas no spin crossover was evidenced in 2. Nearly 1:1 high-spin and low-spin population ratio is found in 3, which remains constant over the entire temperature range investigated.     

Noncollective oblate states in 113Te

High-spin states of 113Te were studied by in-beam spectroscopy using the 88Sr (28Si, 3n) fusion-evaporation reaction at a beam energy of 120 MeV. 7-7, charged particle-7-7 coincidences, and 7-7 angular correlation analyses were employed for determining the level scheme of 113Te. The levels based on the 11/2 - state in 113Te were identified for the first time. The present result of the level scheme of 113Te was in accord with the systematics of those in the heavier isotopes, namely 115Te and 117Te. A particularly favoured 37/2+ state was observed and suggested to be the fully aligned noncollective oblate 7r[(g9/2)2]6+ <8)^[(^5/2) <8s> (h 11/2)2]25/2+ configuration.     

Experimental and numerical modelling of the fluid flow in the continuous casting of steel

This article gives an overview of recent research activities with respect to the mold flow in the continuous casting of steel in presence of DC magnetic fields. The magnetic fields appear to be an attractive tool for controlling the melt flow in a contactless way. Various kinds of magnetic systems are already in operation in industrial steel casting, but the actual impact on the melt flow has not been sufficiently verified by experimental studies. The rapid development of innovative diagnostic techniques in low-melting liquid metals over the last two decades enables new possibilities for systematic flow measurements in liquid metal model experiments. A new research program was initiated at HZDR comprising three experimental facilities providing a LIquid Metal Model for continuous CASTing of steel (LIMMCAST). The facilities operate in a temperature range from room temperature up to 400^°C using the low-melting alloys GaInSn and SnBi, respectively. The experimental program is focused on quantitative flow measurements in the mold, the submerged entry nozzle and the tundish. Local potential probes, Ultrasonic Doppler Velocimetry (UDV) and Contactless Inductive Flow Tomography (CIFT) are employed to measure the melt flow. The behavior of two-phase flows in case of argon injection is investigated by means of the Mutual Inductance Tomography (MIT) and X-ray radioscopy. The experimental results provide a substantial data basis for the validation of related numerical simulations. Numerical calculations were performed with the software package ANSYS-CFX with an implemented RANS-SST turbulence model. The non-isotropic nature of MHD turbulence was taken into account by specific modifications of the turbulence model. First results of the LIMMCAST program reveal important findings such as the peculiar, unexpected phenomenon that the application of a DC magnetic field may excite non-steady, non-isotropic large-scale flow oscillations in the mold. Another important result of our study is that electrical boundary conditions, namely the wall conductivity ratio, have a serious influence on the mold flow while it is exposed to an external magnetic field.     

A Novel Colorimetric and Fluorescent “Off-On” Chemosensor for Cu2+ Based on a Rhodamine Derivative Bearing Naphthyridine Group

A new rhodamine-based derivative bearing a naphthyridine group (compound 1) was synthesized as a colorimetric and fluorescent “off-on” chemosensor for Cu²⁺ in aqueous solutions. The sensing behaviors of 1 toward various metal ions in neutral aqueous solutions were investigated by absorption and fluorescence spectroscopies. Compound 1 is found to exhibit a significant increase in absorbance at 561 nm and an amplified fluorescence at 590 nm toward Cu²⁺ in a selective, sensitive and rapid manner. The quantification of Cu²⁺ by 1 using an absorption spectroscopy method was satisfactory in the linear working range 0.9–10 μM, with a detection limit of 5.4?×?10^?8?M for Cu²⁺ and good tolerance of other metal ions. Upon addition of Cu²⁺, the spirolactam ring (colorless and nonfluorescent) of 1 was opened to ring-opened amide (red color and fluorescent) and a 1:1 stoichiochemetry for the 1-Cu²⁺ complex was formed with an association constant of 1.57?×?10⁴?M^?1.     

A Rhodamine-Based Off�COn Fluorescent Chemosensor for Selectively Sensing Cu(II) in Aqueous Solution

A novel chromogenic and fluorogenic chemosensor RhB-pMOSal comprising a rhodamine fluorophore and a salicylaldehyde receptor being connected by an iminohydrazine link was synthesized and fully characterized. Its sensing behavior toward various metal ions in neutral aqueous solution was investigated by absorption and fluorescence spectroscopy. RhB-pMOSal exhibited a reversible and sensitive ??turn-on?? response of absorption and fluorescence toward Cu²⁺ in aqueous acetonitrile solution. Approximate 65 and 6-fold enhancement in the absorbance at 556 nm and fluorescence intensity at 573 nm were estimated when equivalent Cu²⁺ was added to the RhB-pMOSal solution. Under the same conditions, RhB-pMOSal displayed more sensitive than a reported analogue RhB-Sal to Cu²⁺ ion. The competition experiments for Cu²⁺ mixed with common metal ions exhibited no obvious change in absorption and emission except Cr³⁺ ion that can induce the fluorescence quenching of RhB-pMOSal to some extent.     

Antiproton reflection by a solid surface

The AE?IS experiment (Antimatter Experiment: Gravity, Interferometry, Spectroscopy (Drobychev et al., 2007)), aims at directly measuring the gravitational acceleration g on a beam of cold antihydrogen ( $\overline{\rm H}$ ). After production, the $\overline{\rm H}$ atoms will be driven to fly horizontally with a velocity of a few 100 m/s for a path length of about 1 meter. The small deflection, few tens of μm, will be measured using two material gratings coupled to a position-sensitive detector working as a Moiré deflectometer similarly to what has been done with atoms (Oberthaler et al., Phys Rev A 54:3165, 1996). Details about the detection of the $\overline{\rm H}$ annihilation point at the end of the flight path with a position-sensitive microstrip detector and a silicon tracker system will be discussed.     

Yrast spectroscopy in 49-51Ti via fusion-evaporation reaction induced by a radioactive beam

In-beam $ \gamma$ -ray spectroscopy of high-spin states in ^49-51Ti was performed via the fusion-evaporation reaction using a radioactive beam. By excitation function and $ \gamma$ - $ \gamma$ coincidence analysis, yrast high-spin levels up to I = (21/2^-),(11⁺),(17/2^-) in ^49-51Ti were determined. The levels were compared with full-pf -shell model calculation. The level structure indicates the persistency of the N = 28 shell gap at yrast states in ^49-51Ti .     

Design,synthesis, and biological evaluation of 2-benzylpyrroles and 2-benzoylpyrroles based on structures of insecticidal chlorfenapyr and natural pyrrolomycins

Based on structures of insecticidal chlorfenapyr and antibiotic natural pyrrolomycins, a series of new 2-benzylpyrroles and 2-benzoylpyrroles (with or without ethoxymethyl group on the nitrogen of pyrrole) were designed and synthesized. These compounds or their parent compounds possess weak acidity and high lipophilicity, the two characteristic properties for uncouplers of oxidative phosphorylation; therefore, they are expected to have insecticidal and acaricidal activity. The bioassay result verified that both 2-benzylpyrroles 17 and 2-benzoylpyrroles 19 had varied degrees of insecticidal activity against oriental armyworm depending on the substituents on the benzene ring, but they did not give any acaricidal activity. Conversely, most N-alkylated compounds 18 and 20 exhibited both insecticidal activity and acaricidal activity, of which compound 18i [4-bromo-2-(2,4-dichlorobenzyl)-1-(ethoxymethyl) -5-(trifluoromethyl) - 1 \(H\) -pyrrole-3-carbonitrile] has IC \(_{50}\) as low as 10–20 mg L \(^{-1}\) on both activities.     

Decay of helicity in homogeneous turbulence

The self-similar relaxation of helicity in homogeneous turbulence has been considered taking into account integral invariants ∫ ₀ ^∞ r ^m 〈u(x)ω(x + r)〉 dr = I _m ^h (where ω = curlu and r = |r|). It has been shown that integral invariants with m = 3 for both helicity and energy are possible in addition to helical analogs of Loitsyanskii (m = 4) and Birkhoff-Saffman (m = 2) invariants associated with the conservation laws of momentum and angular momentum, respectively. Helicity always relaxes more rapidly than the energy. Its decay exponent is in the interval from ?3/2 to ?5/2 versus the interval from ?6/5 to ?10/7 for the energy.     

Study on spin configuration in photoresponsive iron mixed-valence complexes by Mössbauer spectroscopy

We have investigated magnetic properties in a series of photoresponsive dithiooxalato (dto)-bridged iron mixed-valence complexes, (SP-R)[Fe^IIFe^III(dto)₃] (SP-R = R-substituted pyridospiropyran cation; R = Me, Et, and Pr; abbreviated as 1 ^Me, 1 ^Et, and 1 ^Pr, respectively). As for our previous reports, 1 ^Me and 1 ^Et show two-step succeeding ferromagnetic transitions at T _C?=?25 & 8 K and 22 & 5 K, respectively. However, 1 ^Et has no hysteresis in the magnetic susceptibility, while 1 ^Me undergoes the charge transfer phase transition with thermal hysteresis around 75 K. To elucidate the two-step transitions of them, we measured ⁵⁷Fe Mössbauer spectra of 1 ^Et. The spectra of Fe^II (S?=?2) and Fe^III (S?=?1/2) in the HTP were observed in the magnetically ordered state as well as the paramagnetic state, and revealed that only HTP exists in a temperature range up to 5 K. The result is consistent with that of 1 ^Pr, where one ferromagnetic phase transition occurs at T _C?=?10 K. ⁵⁷Fe Mössbauer spectroscopy is useful to clarify the origin of the succeeding magnetic transition for these systems.