Electronic charge density and mean kinetic energy of lithium orbitals in LiH,LiH+, Li2, Li2+, LiH2+, and Li2H+

The electron density near the lithium nucleus in the species LiH, LiH⁺, Li₂, Li₂⁺, LiH₂⁺, and Li₂H⁺ was analyzed by transforming the SCF molecular orbitals into a sum of atomic contribnutions, for both core and valence orbitals. These “hybrid-atomic” orbitals were used to compare: electron densities, orbital polarizations, and orbital mean kinetic energies with the corresponding lithium atom quantities. Core-orbital electron densities at the lithium nucleus were observed to increase by up to 0.5% relative to the lithium atom 1s orbital. Lithium cores also exhibited polarization but, surprisingly, in the direction away from the internuclear region. Similar dramatic changes were seen in the electron densities of the valence orbitals of lithium: The electron density at the nucleus for these orbitals increased two-fold for homonuclear species and twenty-fold for heteronuclear triatomic species relative to the electron density at the nucleus in lithium atom. The polarization of the valence orbital electronic charge, in the vicinity of the lithium nucleus, was also away from the internuclear region. The mean “hybrid-atomic” orbital kinetic energies associated with the lithium atom in the molecules also showed changes relative to the free lithium atom. Such changes, accompanying bond formation, were relatively small for the lithium core orbitals (within 0.2% of the value for lithium atom). The orbital kinetic energies for the lithium valence electrons, however, increased considerably relative to the lithium atom: By a factor of about 2 in homonuclear diatomics, by a factor of 7 in heteronuclear diatomics, and by a factor of 11 in the triatomic species. In summary, the total electronic density (core plus valence) at the lithium nucleus remained remarkably constant for all of the species studied, regardless of the effective charge on lithium. Thus, the drastic changes noted in the individual lithium orbitals occurred in a cooperative fashion so as to preserve a constant total electron density in the vicinity of the lithium nucleus. In all cases, bond formation was accompanied by an increase in the orbital kinetic energy of the lithium valence orbital. We suggest that these two observations represent important and significant features of chemical bonding which have not previously been emphasized.     

UO2 2+, Tl+, Pb2+, Ra2+, Bi3+ and Ac3+ adsorption onto polyacrylamide-zeolite composite and its modified composition by phytic acid

The adsorption of naturally occurring radionuclides (UO₂ ²⁺, Tl⁺, Pb²⁺, Ra²⁺, Bi³⁺ and Ac³⁺) onto zeolite (Z) and polyacrylamide-zeolite composite (PAA-Z) and its modified composition by phytic acid (Z-Phy and PAA-Z-Phy) were investigated. Adsorption parameters were derived from the Langmuir and Freundlich fits to adsorption isotherms of the ions studied. The adsorption isotherms were of L and H types. The adsorption capacity of Z decreased by PAA inclusion, but the Phy modification of PAA-Z increased the capacity back to that of Z. The Phy modification made the adsorption spontaneity at least ten times better than in the absence of Phy. This investigation showed that the zeolite, as one of the most abundant natural materials and commonly used adsorbent can also be used for the removal of UO₂ ²⁺ and, in the PAA-Z form, of the studied radionuclides. The usage of Z, as PAA-Z and its Phy modification provide research materials which possess adequate practicality and effectiveness in studies of adsorption. This revised version was published online in July 2006 with corrections to the Cover Date.     

Separation of strontium from simulated waste in K2SO4/Nitrate medium containing Sr2+, Eu3+, Ce3+, Pd2+, Rh3+, Ru3+, UO 2 2+ , Fe3+, Cr3+, Ni2+, Al3+, Ca2+ and Cs+, by strongly basic anion exchanger

In this work Strontium was separated selectively form, Pd²⁺, Ni²⁺ and Ca³⁺ using anionic resins of Amberlite type IRA-900 and IRA-410 from nitrate medium. The Separation of strontium by strongly basic anion exchangers IRA-410 and IRA-900 from simulated waste containing, Sr²⁺, Eu³⁺, Ce³⁺, Pd²⁺, Rh³⁺, Ru³⁺, VO₂ ²⁺, Fe³⁺, Cr³⁺, Ni²⁺, Al³⁺, Ca²⁺, and Cs⁺, in K₂SO₄/nitrate medium which adsorbed as strontium sulphate complex was achieved through ligand- ligan exchange. The elution of strontium carried out via “loading” the column with a solution of 0.03N EDTA in presence of 0.1N NaNO₃ at pH7 where Sr²⁺ has low K_d value. An inductively Coubled Plasma — Optical Emission Spectrometry (ICP — OES) of ARL type model 3520, was used for elemental analysis.     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

Understanding the inactivation process of organophosphorus herbicides: A DFT study of glyphosate metallic complexes with Zn2+, Ca2+, Mg2+, Cu2+, Co3+, Fe3+, Cr3+, and Al3+

Glyphosate is the active component of one of the top‐selling herbicides, which is also a potent EPSP synthase inhibitor. The herbicide is absorbed by living tissue and translocated via the phloem, to plant roots and rhizomes. When applied directly into the soil it has low activity, due to the high adsorption by soil constituents. Understanding the specific interactions between metals in the soil and glyphosate is the main step in understanding the low activity of the herbicide when applied directly into the ground and not pulverized. We can observe there is a stability order for both tetrahedral and octahedral complexes between glyphosate and metals: Zn>Cu>Co>Fe>Cr>Al>Ca>Mg. © 2012 Wiley Periodicals, Inc.     

A photoelectron photoion coincidence study of the vinyl bromide and tribromoethane ion dissociation dynamics: heats of formation of C2H3+, C2H3Br, C2H3Br+, C2H3Br2+, and C2H3Br3

The threshold photoelectron photoion coincidence (TPEPICO) technique has been used to measure accurate dissociative photoionization onsets of vinyl bromide and 1,1,2-tribromoethane. The reactions investigated and their 0 K onsets are C2H3Br + hnu --> C2H3+ + Br (11.902 +/- 0.008 eV); C2H3Br3 + hnu --> C2H3Br2+ + Br (10.608 +/- 0.008 eV); and (C2H3Br3 + hnu --> C2H3Br+ + 2Br (12.301 +/- 0.035 eV). The vinyl ion heat of formation (Delta(f)H degrees 298K = 1116.1 +/- 3.0 kJ/mol) has been calculated using W1 theory and used as an anchor along with the measured dissociation energies to determine the heats of formation, Delta(f)H degrees 298K, in kJ/mol, of the following bromine-containing species: C2H3Br (74.1 +/- 3.1), C2H3Br+ (1021.9 +/- 3.1), C2H3Br2+ (967.1 +/- 4.0), and C2H3Br3 (53.5 +/- 4.3). These results represent accurate and consistent experimental determinations of heats of formation for these bromine-containing species, which serve to correct the discrepancies in the literature for C2H3Br and C2H3Br+ and provide the first experimental determination for the enthalpies of formation of C2H3Br2+ and C2H3Br3.     

Electronic transition and energy transfer processes in LaPO4-Ce3+/Tb3+ nanowires

Ce3+ and Tb3+ coactivated LaPO4 nanowires and micrometer rods were synthesized by hydrothermal methods. Their fluorescent spectra and dynamics were systematically studied and compared. The results indicated that the extinction coefficients of Ce3+ and Tb3+ in nanowires were higher than those in micrometer rods. The electronic transition rates of Ce3+ and Tb3+ in nanowires had little variation in contrast to those in micrometer rods, and the energy transfer rate and efficiency of Ce3+ --> Tb3+ in nanowires were reduced greatly. It is important to observe that the brightness for the 5D4-7F5 green emissions of Tb3+ via energy transfer of Ce3+ --> Tb3+ in nanowires increased several times that in micrometer rods. This was attributed to the decreased energy loss in the excited states, being higher than 5D4 due to the hindrance of the boundary.     

Vacuum ultraviolet photon emission stimulated by H2+, N2+, and CO+ collisions with surfaces

Intravalence and Rydberg-type electronic transitions from excited projectile atoms and ions have been observed in the spectral range 30-200 nm as a result of 3 keV H⁺₂, N⁺₂, and CO⁺ bombardment of magnesium and graphite surfaces. Population of both types of excited states is consistent with an electron promotion mechanism resulting from close atomic encounters.     

Infrared spectra of chlorinated ethylene cations: C2Cl4+, C2HCl3+, 1,1-C2H2Cl2+, and trans-C2H2Cl2+ in solid argon

Infrared spectra of chlorinated ethylene cations: C2Cl4+, C2HCl3+, 1,1-C2H2Cl2+, and trans-C2H2Cl2+ isolated in solid argon are presented. These cations were produced by co-deposition of chlorinated ethylene/Ar mixtures with high-frequency-discharged Ar at 4 K. Photosensitive absorptions are assigned to different vibrational modes of the cations on the basis of observed chlorine isotopic shifts and quantum chemical frequency calculations. With the removal of one electron from the HOMO of chlorinated ethylene neutrals that is C=C bonding and C-Cl antibonding in character, the observed C-Cl stretching vibrational frequencies of the cations are blue-shifted relative to those of the chlorinated ethylene neutrals. The results also show that the cations can be regarded as "isolated" with the vibrational frequencies only slightly shifted when compared to the available gas-phase values.     

Adsorption of UO2 2+, Tl+, Pb2+, Ra2+ and Ac3+ onto polyacrylamide-bentonite composite

Composite of polyacrylamide-bentonite (PAA-B) was prepared by direct polymerization in a suspension of bentonite (B), the composite was then modified by phytic acid (PAA-B-Phy). The parameters related to adsorption of UO₂ ²⁺ in absence and presence of 0.01M CaCl₂ and of natural radionuclides (Tl⁺, Pb²⁺, Ra²⁺ and Ac³⁺ in a leaching solution) onto PAA-B and PAA-B-Phy, and thermodynamics of the adsorption were investigated. Adsorption isotherms were of L and H types for the adsorption of UO₂ ²⁺ onto PAA-B and PAA-B-Phy, whilst for Tl⁺, Pb²⁺, Ra²⁺ and Ac³⁺ they were of C type for both adsorbents. Langmuir equilibrium constants for the adsorption of all studied ions onto PAA-B-Phy were significantly higher than those found for PAA-B. The thermodynamic parameters indicated that adsorption reactions are spontaneous in terms of adsorption free enthalpy. The composite of PAA-B and its modification by Phy have been used for the first time in this study. It is concluded that the composites can be practically used for adsorption and applied as adsorbent of radionuclides.     

Electron spin resonance study on H6+, H5D+, H4D2+, and H2D4+ in solid parahydrogen

We carried out an electron spin resonance (ESR) study on hydrogen ion radicals produced by radiolysis of solid para-H(2). In addition to quartet ESR lines proposed to be H(2) (+)-core H(6) (+) (D(2d)) ions in solid para-H(2) [T. Kumada et al., Phys. Chem. Chem. Phys. 7, 776 (2005)], we newly observed totally more than 50 resolved lines in gamma-ray irradiated solid para-H(2)-ortho-D(2) (1 mol %) and para-H(2)-HD (1 mol %) mixtures. We assigned these lines to be isotope substituents of H(2) (+)-core H(6) (+) ions such as H(5)D(+), H(4)D(2) (+), and H(2)D(4) (+) throughout the comparison of their ESR parameters with theoretical results. These results provide a conclusive evidence that H(2) (+)-core H(6) (+) ions are generated in irradiated solid hydrogens. Analysis of the EPR spectrum and ab initio calculations predicts D(2d) symmetry of the H(6) (+) ions, whereas a lowering symmetry (D(2d)-->C(2v)) induced by asymmetric nuclear wave function is observed in H(5)D(+) and H(4)D(2) (+). We also observed isotope-substitution reactions such as H(6) (+)+D(2)-->H(4)D(2) (+)+H(2) and H(6) (+)+HD-->H(5)D(+)+H(2), which are analogous to the well-known isotope-condensation reactions of H(3) (+) in dark nebula, H(3) (+)+HD-->HD(2) (+)+H(2) and HD(2) (+)+HD-->D(3) (+)+H(2).     

Competitive uptake of labelled Cs+, Ba2+ and Zn2+ ions by zeolite-3A

Competitive uptake of Cs⁺, Ba²⁺ and Zn²⁺ ions from aqueous medium by zeolite-3A is studied by the radiotracer technique. Suppression Cs⁺ uptake in presence of Ba²⁺ is the maximum amongst the competitive uptakes. The simultaneous uptakes of the individual cations are considered in the light of the zeolite pore size, hydration effects and mobilities of the competing cations.     

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.