High-resolution mass spectrometric study of pure helium droplets,and droplets doped with krypton

Mass spectra of doped and undoped helium droplets are presented. The high resolution of the time-of-flight spectrometer (m/Δm ≅ 5000) makes it possible to fully resolve small helium cluster ions from impurities and to unambiguously identify abundance anomalies in the size distribution of He _n ⁺. The yield of He₄ ⁺ shows the well-known enhancement relative to other small cluster ions when the expansion changes from sub- to supercritical, provided the electron energy exceeds a value of 40 ± 1 eV, the threshold for formation of electronically excited ions. Upon doping with krypton, pure Kr _n ⁺ cluster ions containing up to 41 Kr atoms are observed. The spectra exhibit abundance anomalies at 13, 16, 19, 22 & 23, 26 and 29, in agreement with spectra obtained by ionization of bare krypton clusters that are formed in neat supersonic beams. Mixed clusters He _m Kr⁺ indicate closure of a solvation shell at m = 12.     

Origin of threshold electrons produced in decay of the Xe 4d−1 np resonance

Coincidence spectra of energetic electrons with threshold electrons were measured following photo-excitation of the Xe 4d_3/2, 5/2 → np resonances, in order to investigate the origin of threshold electrons, and the mechanism leading to formation of the Xe²⁺ 5p⁻² and 5s⁻¹5p⁻¹ final states. A two-step decay process was observed in the production of Xe²⁺ 5p⁻²(¹D) following decay of the 7p resonance, where the intermediate state is Xe^+* 5p⁻²(¹S)8p that autoionizes emitting a pseudo-threshold electron. This process was confirmed in a time-of-flight analysis of the coincidence spectra of the energetic electrons with the threshold photoelectrons. It is suggested that a similar two-step process also contributes to the population of excited Xe²⁺ states and is the main origin for the production of threshold electrons in decay of the 4d⁻¹ np resonances.     

Resonances and chaos in the collinear collision system (He,H 2 + ) and its isotopic variants

The collinear atom-diatom collision system provides one of the simplest instances of chaotic or irregular scattering. Classically, irregular scattering is manifest in the sensitive dependence of post-collision variables on initial conditions, and quantally, in the appearance of a dense spectrum of dynamical resonances. We examine the influence of kinematic factors on such dynamical resonances in collinear (He, H ₂ ⁺ ) collisions by computing the transition state spectra for collinear (He, HD⁺) and (He, DH⁺) collisions using the time-dependent quantum mechanical approach. The nearest neighbor spacing distributionP(s) and the spectral rigidity Δ₃(L) for these resonances suggest that the dynamics is predominantlyirregular for collinear (He, HD⁺) and predominantlyregular for collinear (He, DH⁺). These findings are reinforced by a significantly larger “correlation hole” in ensemble averaged survival probability ≪P(t)≫ values for collinear (He, HD⁺) than for collinear (He,DH⁺). In addition we have also examined measures of classical chaos through the dependence of the final vibrational action,n _f, on the initial vibrational phaseφ _i of the diatom, and Poincaré surfaces-of-section. They show that (He, HD⁺) collisions are partly chaotic over the entire energy range (0–2.78 eV) while (He, DH⁺) collisions, in contrast, are highly regular at collision energies below the classical threshold for reaction. Above the threshold, the scattering remains regular for initial vibrational statesv=0 and 1 of DH⁺.     

Plasma-filled rippled wall rectangular backward wave oscillator driven by sheet electron beam

Performance of the backward wave oscillator (BWO) is greatly enhanced with the introduction of plasma. Linear theory of the dispersion relation and the growth rate have been derived and analysed numerically for plasma-filled rippled wall rectangular waveguide driven by sheet electron beam. To see the effect of plasma on the TM₀₁ cold wave structure mode and on the generated frequency, the parameters used are: relativistic factor γ = 1.5 (i.e. v/c = 0.741), average waveguide height y ₀ = 1.445 cm, axial corrugation period z ₀ = 1.67 cm, and corrugation amplitude ε = 0.225 cm. The plasma density is varied from zero to 2 ×10¹² cm^− 3. The presence of plasma tends to raise the TM₀₁ mode cut-off frequency (14 GHz at 2 ×10¹² cm^− 3 plasma density) relative to the vacuum cut-off frequency (5 GHz) which also causes a decrease in the group velocity everywhere, resulting in a flattening of the dispersion relation. With the introduction of plasma, an enhancement in absolute instability was observed.     

Spectrum of the H− Ion in the s-Wave Model

 The H⁻ ion in the s-wave model has one bound state and a Rydberg series of resonances, one associated with each inelastic threshold of the electron hydrogen system. We calculate the energy of the bound state and the energies of the resonances as well as their total widths up to N = 9 and partial widths up to N = 7. Received July 5, 1999; revised February 18, 2000; accepted for publication February 22, 2000     

Electron impact ionization of atomic clusters in ultraintense laser fields

In this paper we report on inner ionization of Xe_n clusters (n = 55- 2171) in ultraintense Gaussian laser fields (peak intensity I = 10¹⁵- 10²⁰ Wcm^-2, pulse width τ= 25 fs, frequency 0.35 fs^-1). The cluster inner ionization process is induced by the barrier suppression ionization (BSI) mechanism and by electron impact ionization (EII), which occurs sequentially with the BSI. We address electron impact ionization of clusters, which pertains to inelastic reactive processes of the high-energy (100 eV–1 keV per electron) nanoplasma. We utilized experimental data for the energy dependence of the electron impact ionization cross-sections of Xe^j+ (j = 1-10) ions, which were fit by an empirical three-parameter Lotz-type equation, to explore EII in clusters by molecular dynamics simulations. Information was obtained on the yields and time-resolved dynamics of the EII levels (i.e., number n_imp of electrons per cluster atom) in the Xe_n clusters and their dependence on the laser intensity and cluster size. The relative long-time (t = 90 fs) yields for EII, n_imp/n_ii (where n_ii is the total inner ionization yield) are rather low and increase with decreasing the laser intensity. In the intensity range I = 10¹⁵-10¹⁶ Wcm^-2, n_imp/n_ii = 0.21 for n = 2171 and n_imp/n_ii = 0.09-0.14 for n = 459, while for I = 10¹⁸-10²⁰ Wcm^-2, n_imp/n_ii = 0.01-0.05. The difference Δn_imp between the EII yield at long time and at the termination of the laser pulse reflects on ionization dynamics by the nanoplasma when the laser pulse is switched off. For Xe₂₁₇₁ in the lower intensity domain, Δ n_imp = 0.9 at I = 10¹⁵ Wcm^-2 and Δn_imp = 0.4 at 10¹⁶ Wcm^-2, reflecting on EII by the persistent nanoplasma under “laser free” conditions, while in the higher intensity domain of I = 10¹⁷ - 10¹⁸ Wcm^-2, Δn_imp is negligibly small due to the depletion of the transient nanoplasma.     

Fluorescent Properties of a Hybrid Cadmium Sulfide-Dendrimer Nanocomposite and its Quenching with Nitromethane

A fluorescent hybrid cadmium sulphide quantum dots (QDs) dendrimer nanocomposite (DAB-CdS) synthesised in water and stable in aqueous solution is described. The dendrimer, DAB-G5 dendrimer (polypropylenimine tetrahexacontaamine) generation 5, a diaminobutene core with 64 amine terminal primary groups. The maximum of the excitation and emission spectra, Stokes’ shift and the emission full width of half maximum of this nanocomposite are, respectively: 351, 535, 204 and 212 nm. The fluorescence time decay was complex and a four component decay time model originated a good fit (χ = 1.20) with the following lifetimes: τ ₁ = 657 ps; τ ₂ = 10.0 ns; τ ₃ = 59.42 ns; and τ ₄ = 265 ns. The fluorescence intensity of the nanocomposite is markedly quenched by the presence of nitromethane with a dynamic Stern-Volmer constant of 25 M⁻¹. The quenching profiles show that about 81% of the CdS QDs are located in the external layer of the dendrimer accessible to the quencher. PARAFAC analysis of the excitation emission matrices (EEM) acquired as function of the nitromethane concentration showed a trilinear data structure with only one linearly independent component describing the quenching which allows robust estimation of the excitation and emission spectra and of the quenching profiles. This water soluble and fluorescent nanocomposite shows a set of favourable properties to its use in sensor applications.     

Cluster radioactivity leading to doubly magic <Superscript>100</Superscript>Sn and <Superscript>132</Superscript>Sn daughters

Decay of neutron-deficient ^{128 − 137}Gd parents emitting ⁴He to ³²S clusters are studied within the Coulomb and proximity potential model. The predicted half-lives are compared with other models and most of the values are well within the present experimental limit for measurements (T _1/2 < 10³⁰ s). The lowest T _1/2 value for ²⁸Si emission from ¹²⁸Gd indicates the role of doubly magic ¹⁰⁰Sn daughter in cluster decay process. It is also found that neutron excess in the parent nuclei slows down the cluster decay process. Geiger–Nuttal plots for all clusters are found to be linear with different slopes and intercepts. The α-decay half-lives of ^{148 − 152}Gd parents are computed and are in agreement with experimental data. The role of doubly magic ¹³²Sn daughter in cluster decay process is also examined for various neutron-rich Ba, Ce, Nd, Sm and Gd parents emitting clusters ranging from ⁴He to ³²Si. Alpha-like structures are most probable in the decays leading to ¹⁰⁰Sn, while non-α-like structures are probable in the decays leading to ¹³²Sn. The neutron–proton asymmetry in parent and daughter nuclei is responsible for the reduced decay rate in the decay leading to ¹³²Sn.     

Optical absorption behavior of Tl<Superscript>+</Superscript> DOPED Rb(Br<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>I<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>) system

The optical absorption behavior of Tl⁺ doped Rb(Br_1–x I _x ) mixed crystals (with x = 0.00, 0.05, and 0.10) grown under vacuum by slow cooling from the melt has been studied. Absorption spectra of the mixed crystals recorded at room temperature showed that the characteristic A-absorption band of Tl⁺ ions in the Rb(Br_1–x I _x ) system (0.1 mol. %) with x = 0.00 (i.e., RbBr:Tl⁺) broadened with the iodine content towards the low energy side. Changes in the absorption spectra of the mixed crystals are due to creation of some complex centers involving Tl⁺, Br^–, and I^- ions with energy levels inside the band gap while forming the mixed crystal. The absorption spectra of gamma-irradiated mixed crystals showed the F-band, which shifted towards the low energy side due to the existence of iodine ions in the mixed crystals.     

Vibrational wave packet dynamics in the silver tetramer probed by NeNePo femtosecond pump-probe spectroscopy

We present results on the ultrafast dynamics of mass-selected neutral Ag₄ clusters using NeNePo (negative ion - neutral - positive ion) femtosecond pump-probe spectroscopy. One-color pump-probe spectra of the Ag₄ ^-/Ag₄/Ag₄ ⁺ system measured at 385 nm and an internal cluster temperature of 20 K display a complex beat structure over more than 60 ps. The oscillatory structure is attributed to vibrational wave packet dynamics in an excited “dark" state of neutral Ag₄. A dominant 740 fs wave packet period as well as wave packet dephasing and rephasing are observed in the spectra. Fourier analysis of the spectra yields a group of frequencies centered around 45 cm^-1 and an anharmonicity χ _e2νχ _eχ _e of 2.65 cm^-1 for the active vibrational mode. Received 30 November 2000     

Femtosecond ionization of magnesium clusters grown in ultracold helium droplets

Magnesium clusters grown in helium droplets and ionized with femtosecond laser pulses have been studied by high resolution mass spectrometry. For moderate laser intensities the abundance spectra show characteristic features indicating electronic shell effects. Compared to clusters of s¹-electron metals additional shell closures appear resulting from an electron rearrangement. Irradiation with higher laser intensities leads to a decomposition of the magnesium clusters into atomic ions. Due to charge exchange with the surrounding helium matrix mainly singly and doubly charged magnesium ions remain. In addition, the occurrence of MgHe_N ⁺-complexes is observed. Their abundance depends on the shape of the laser field, i.e. the laser width and the optical delay when applying the pump-probe technique. Received 2 January 2001     

Fluorescent Carbon Dots Capped with PEG<Subscript>200</Subscript> and Mercaptosuccinic Acid

The synthesis and functionalization of carbon nanoparticles with PEG₂₀₀ and mercaptosuccinic acid, rendering fluorescent carbon dots, is described. Fluorescent carbon dots (maximum excitation and emission at 320 and 430 nm, respectively) with average dimension 267 nm were obtained. The lifetime decay of the functionalized carbon dots is complex and a three component decay time model originated a good fit with the following lifetimes: τ ₁ = 2.71 ns; τ ₂ = 7.36 ns; τ ₃ = 0.38 ns. The fluorescence intensity of the carbon dots is affected by the solvent, pH (apparent pK _a of 7.4 ± 0.2) and iodide (Stern-Volmer constant of 78 ± 2 M⁻¹).     

Nonlinear transformation of a spectrum of femtosecond laser pulses in a gas-filled microcapillary

Features of light pulse propagation and nonlinear optical transformation of the spectrum generated by titanium-sapphire laser pulses (τ_0.5 = 27 fs, λ₀ = 790 nm) have been studied experimentally in a 50-cm cylindrical hollow waveguide (microcapillary with 280-μm diameter core) filled with gaseous molecular nitrogen and helium. Stable guided propagation of light pulses with an intensity of ~1.5⋅10¹⁴ W/cm² in the fundamental EH₁₁ mode of the gas-filled capillary has been demonstrated. Exact focusing of the laser light made it possible to obtain rather high relative (≥95%) and absolute (~60%) energy transmission efficiencies for the pulses at gas pressures equal to or lower than 760 Torr. A method to determine the nonlinear phase shift of the pulses has been proposed. Values of the nonlinear refractive index n₂ ≈ 4.5⋅10^–23 cm²/(W⋅Torr) (N₂) and n₂ ≈ 2.8⋅10^–23 cm²/(W⋅Torr) (He) have been found. A short-wavelength shift in addition to the Kerr nonlinearity has been shown to be contributed by the generated electron plasma at high pulse intensities (≥10¹⁴ W/cm²).     

Luminescent properties of YVO4:Eu/SiO2 core–shell composite particles

We report an efficient process for preparing monodisperse SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors using a simple citrate sol–gel method and without the use of surface-coupling silane agents or large stabilizers. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectra were used to characterize the resulting SiO₂@Y_0.95Eu_0.05VO₄ core–shell phosphors. The XRD results demonstrate that the Y_0.95Eu_0.05VO₄ particles crystallization on the surface of SiO₂ annealing at 800 °C is perfectly and the crystallinity increases with raising the annealing temperature. The obtained core–shell phosphors have a near perfect spherical shape with narrow size distribution (average size ca. 500 nm and an average thickness of ~50 nm), are not agglomerated, and have a smooth surface. The thickness of the YVO₄:Eu³⁺ shells on the SiO₂ cores could be easily tailored by changing the mass ratio of shell to core (W = [YVO₄]/[SiO₂]) (~50 nm for W = 30%). The Eu³⁺ shows a strong PL luminescence (dominated by ⁵D₀ − ⁷F₂ red emission at 618 nm) under the excitation of 320 nm UV light. The PL intensity of Eu³⁺ increases with increasing the annealing temperature and the values of W.     

Projectile charge and velocity effect on UO2 sputtering in the nuclear stopping regime

Angular distributions and yields of uranium sputtered by slow highly charged Xe^q+ ions (kinetic energy 1.5 keV ￡ E_k ￡ 811.5~{\rm keV}\le E_{k}\le 81  keV, charge state 1≤q≤25) from UO₂ were measured by means of the catcher technique. A charge state effect on the sputtering process is observed at 8 and 81 keV. A deviation from a Acosθ shape (the linear collision cascade theory) is observed in case of Xe^q+ impinging a UO₂ surface at E_k=8 keV. Yields increase linearly with projectile charge state q thus clearly revealing the contribution of potential energy to the sputtering process. In addition, as the kinetic energy of a Xe¹⁰⁺ projectile decreases from 81 keV to 1.5 keV, a velocity effect is clearly observed on the angular distribution.     

Fluorescent Property of the Gd<Superscript>3+</Superscript>-Doped Terbium Complexes and Crystal Structure of [Tb(TPTZ)(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]Cl<Subscript>3</Subscript>·3H<Subscript>2</Subscript>O

The complex of Tb(TPTZ)Cl₃·3H₂O was synthesized by adding the ethyl alcohol solution of TbCl₃ (1 mmol) to the solution of 2,4,6-tris-(2-pyridyl)-s-triazine(TPTZ,1 mmol) with constant stirring. The solution which had been filtered was kept at the room temperature for 4 weeks, and then a kind of transparent crystal was formed. Besides, nine kinds of solid complexes in the different molar proportion of terbium to gadolinium had been synthesized by adopting the similar method mentioned above. It was inferred from the elemental analysis and rare earth complexometry that the composition of these complexes is (Tb_xGd_y)(TPTZ)Cl₃·3H₂O (x : y = 0.9 : 0.1, 0.8 : 0.2, 0.7 : 0.3, 0.6 : 0.4, 0.5 : 0.5, 0.4 : 0.6, 0.3 : 0.7, 0.2 : 0.8, 0.1 : 0.9). The absorption spectra and photoluminescence of the complexes were determined in dimethylsulfoxide (DMF), which showed that the excitation of the complexes is mostly ligand based. The triplet state energy level of TPTZ was measured, indicating that the lowest excitation state energy level of Tb(III) and the triplet state energy level of TPTZ match well each other. The fluorescent data indicated that the fluorescent emission intensity of Tb³⁺ ions would be enhanced in the complexes after terbium was doped with Gd³⁺ ion. When x : y was 0.5 : 0.5, the fluorescent emission intensity was the largest. The result obtained by testing the X-ray diffraction of the monocrystal revealed that the molecular formula of the mono-crystal complex is [Tb(TPTZ)(H₂O)₆]Cl₃·3H₂O. The number of metal ion coordinates is nine, and the tridentate TPTZ and six water molecules are bonded with terbium respectively. Besides, it also revealed that the monocrystal belongs to the monoclinic system, and space group Cc with the following unit cell parameters is a = 1.4785 (3) nm, b = 1.0547 (2) nm, c = 1.7385 (4) nm, β = 94.42 (3)°, V = 2.7028 (9) nm³ and Z = 4.     

Damping of the localized surface plasmon polariton resonance of gold nanoparticles

We report on a strong damping of the localized surface plasmon polariton resonance of gold nanoparticles. The ultra-fast dephasing time of localized surface plasmon polariton resonances in gold nanoparticles was systematically studied as a function of the particle size at a fixed photon energy of h ν=1.85 eV. Dephasing times ranging from T₂^expT_{2}^{\mathrm{exp}} = 5.5 fs to 15.0 fs were extracted and an influence of the reduced dimensions was detected. We have identified two dominant damping mechanisms: the well-known surface scattering and, for the first time, band structure changes. We have quantified the influence of these band structure changes on the optical properties by determining the essential damping parameter A to be A ^exp=0.32 nm/fs.     

Reductive Fluorescence Quenching of the Photoexcited Free Base <Emphasis Type="Italic">meso</Emphasis>-Tetrakis (Pentafluorophenyl) Porphyrin by Amines

Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H₂F₂₀TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H₂F₂₀TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime τ _f = 9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H₂F₂₀TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H₂F₂₀TPP. The fluorescence quenching rate constants ranged from 1 × 10⁹ to 4 × 10⁹ s⁻¹, which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern–Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H₂F₂₀TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (∆G⁰) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.     

Adsorption and thermodynamics studies of U(VI) by composite adsorbent in a batch system

The adsorption of U(VI) from aqueous solutions onto composite adsorbent (algistar) has been studied using a batch adsorber. The parameters that affect the U(VI) sorption, such as contact time, solution pH, initial U(VI) concentration, and temperature, have been investigated and optimized conditions determined. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of composite adsorbent, and experimental results showed this to be 43.10 mg/g. The adsorption patterns of metal ions on composite adsorbent followed the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherms. The Freundlich, Langmuir, and D–R models have been applied, and the data correlate well with Langmuir model, and that the sorption is physical in nature (the sorption energy E _ads = 12.90 kJ/mol). Thermodynamic parameters (∆H _ads^o = −41.08 kJ/mol, ∆S _ads^o = −68.00 J/mol K, ∆G _ads (298.15 K) = −20.81 kJ/mol) showed the exothermic heat of adsorption and the feasibility of the process. The results suggested that the composite adsorbent is suitable as a sorbent material for recovery and biosorption/adsorption of uranium ions from aqueous solutions.     

A comparative study of solid-silver and silver-shell nanodimers on surface plasmon resonances

We investigated numerically the scattering cross sections and near-field intensities of solid-silver and silver-shell (shell thickness d = 10 nm) nanodimers that interact with incident plane wave by the use of finite-element method with three-dimensional models. Results show that the silver-shell cases exhibit tunable surface plasmon resonances and its rotational effects can induce more surface plasmons in a wider range of wavelength that are not observed for the solid-silver cases with the same volume (1,046,666 nm³).