On the determination of HCl+ (A,v′) vibrational populations from HCl+ (A→X) fluorescence spectra: direct comparison between photoionization and penning ionization

Using a beam apparatus, we have measured the HCl⁺ (A,v′→X,v″) fluorescence spectra of HCl⁺ (A,v′) ions formed in HeI (58.4 nm), and NeI (73.6 nm) photoionization and, for the first time, in He (2³ S) Penning ionization under single collision conditions with a wavelength bandwidth around 1 nm. In addition, we have studied Ne (3s ³ P _{2, 0}) Penning ionization of HCl at three different collision energies. The procedure and the problems in extracting HCl⁺ (A,v′) vibrational populations from the data are discussed in some detail. Thedirect comparison of photoionization and Penning ionization data allows definitive conclusions to be drawn on the question whether final state interactions in the Penning reaction change the “nascent” vibrational population (determined by electron spectrometry); for He (2³ S)+HCl, such changes are shown to be absent within the experimental uncertainty (<±10%). For Ne (3s ³ P _{2, 0})+HCl, the HCl⁺ (A,v′=0, 1) populations are also found to be close to those measured by electron spectrometry and essentially independent of collision energy in the range 34–96 meV. From measurements of the fluorescence intensity as a function of HCl density, we have evidence for a fast loss of HCl⁺ (A,v′) ions in collisions with HCl (rate constant around 5·10^?9 cm³s^?1).     

Penning ionization electron spectrometry of hydrogen chloride

An electron spectrometric study has been performed on HCl using metastable helium and neon atoms as well as neon resonance photons. High resolution electron spectra were obtained with two different beam apparatuses for a mixed He(2¹ S, 2³ S) beam, a pure He(2³ S) beam, and, for the first time, state-selected pure Ne(3s ³ P ₂) and pure Ne(3s ³ P ₀) beams, and for NeI resonance photons. For the system He(2³ S)+HCl the vibrational populationsP(υ′) of the formed HCl⁺ (X ²∏ _i , υ′) and HCl⁺ (A ²Ω⁺, υ′) ions are found to differ from the Franck-Condon factors for unperturbed potentials, indicating slight bond stretching in HCl upon He(2³ S) approach. For He(2¹ S)+HCl the vibrational peak shapes and vibrational populations are substantially different from the He(2³ S) case, pointing to an additional, charge exchanged interaction (He⁺+HCl^?) in the entrance channel of the former system. For the first time, we have detected the electrons in both the He(2¹ S)+HCl and He(2³ S)+HCl spectra associated with the major mechanism for the formation of Cl⁺ ions: energy transfer to repulsive HCl** Rydberg states, dissociating toH(1s) and autoionizing Cl**(¹ D ₂ nl) atoms. For both Ne(³ P ₂)+HCl and Ne(³ P ₀)+HCl, the populationsP(υ′) of both final molecular states HCl⁺ (X, A) agree closely with the Franck-Condon factors at the average relative collision energyē _coll=55 meV and, for HCl⁺ (A ²Ω⁺), also atē _coll=130 meV.     

Chlorine K shell photoabsorption spectra of gas phase HCl and Cl2 molecules

High resolution photoabsorption spectra of HCl and Cl₂ have been measured near the chlorineK edge in the 2810–2850 eV photon energy range. Below the ClK edge, the strongest resonance is interpreted as a simple core excitation into the unoccupied σ* valence orbital for both molecules, leading to a markedly repulsive state. Higher resonances due to low lying Rydberg states, are observed in both systems, but with a larger oscillator strength for HCl as compared to Cl₂. In Cl₂, the σ* orbital is deep enough to avoid any mixing with Rydberg orbitals. In HCl, we observe the dipole forbidden Cl 1s → 4s transition which denotes a strong 4s–4p hybridization. Above the ClK edge, the multiplet features seen for HCl are analysed in terms of double-core-valence excited vacancy states. In Cl₂, their counterpart are found very close to the ionization threshold because of the deep σ* orbital and possibly because the excited core and valence electrons originates either from the same atomic site or from different ones.     

Discrimination ofn=2→2 UV transitions of he-like ions in a recoil light source

Neon and argon recoil ions were produced by collisions with 5.9 MeV/amu uranium projectiles andΔn=0 ultraviolet transitions from the metastable 1s2p ³ P _0,2 levels of the target ions were measured in delay to the pulsed projectile beam.     

Removal of ammonium ion from aqueous solutions using natural zeolite: kinetic,equilibrium and thermodynamic studies

The aim of the present study is to investigate the removal of ammonium ions from aqueous solutions using the natural Western Azerbaijan zeolite by utilizing ion exchange process. Batch experimental studies were conducted to evaluate by changing relevant parameters such as pH, dosage of adsorbent, stirring time, initial ammonium concentration, and temperature. The results clearly confirmed that all mentioned parameters have vital affects on removing ammonium ions from wastewater and effluents, so got optimized. Adsorption kinetics and equilibrium data for the removal of ammonium ion were analyzed using Langmuir and Freundlich equations. The Langmuir model fits the equilibrium data better than the Freundlich model. According to the Langmuir equation, the maximum uptake for ammonium ion was 43.47 (mg g^?1). Pseudo-first-order and pseudo-second-order models were used to represent the kinetics of the process. Kinetic studies showed that the adsorption followed a pseudo-second-order reaction. The calculated thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicate that the adsorption process is feasible, spontaneous, and endothermic at 20–50 °C. Based on the experimental results, it can be suggested that the natural Western Azerbaijan zeolite has the potential of application as an efficient adsorbent for the removal of ammonium ions from aqueous solutions, and is suggested for wastewater treatment purposes.     

Electron attachment to HCl clusters

Negatively charged cluster ions of hydrogen chloride are formed by electron attachment to HCl clusters, which are produced in a seeded supersonic beam traversing a sustained gas discharge. Cluster ions of (HCl) _n ^? , withn=2, and tentatively withn=3 and 4 are observed. Cluster ions like Cl _n ^? , Cl _n ^? (HCl) _m , and withAr attached to them are also seen. The relevance to radiation chemistry of HCl if briefly discussed. Atoms evaporating from the hot, thoriated tungsten filament of the glow discharge lead to clusters such as Th _n ^? and its oxides.     

Molecular structure,quantum chemical investigation,and thermal behavior of (DNAZ-CO)<Subscript>2</Subscript>

Bis-(3,3-dinitroazetidinyl)-oxamide ((DNAZ-CO)₂) is an acyl derivative of 3,3-dinitroazetidine (DNAZ). It is prepared and its crystal structure is determined. The crystal is orthorhombic, Fdd2 space group, a = 13.136(14) Å, b = 19.48(3) Å, c = 10.326(14) Å, V = 2642 (6) ų, Z = 8. A density functional theory (DFT) method of the Amsterdam Density Functional (ADF) package is used to calculate the geometry, frequencies, and properties. The optimized geometry, frontier orbital energy, and main atomic orbital percentage are obtained. The thermal behavior is studied under a non-isothermal condition by DSC and TG/DTG methods. The apparent activation energy (E _a) and pre-exponential factor (A) of the exothermic decomposition reaction of (DNAZ-CO)₂ are 164.10 kJmol^?1 and 10^13.38 s^?1 respectively. The critical temperature of thermal explosion is 272.20°C. The values of ΔS ^≠, ΔH ^≠, and ΔG ^≠ of this reaction are 6.44 Jmol^?1·K^?1, 163.76 kJmol^?1 and 160.34 kJmol^?1 respectively.     

The special features of formation of nanotubes and mesoporous materials on the basis of vanadium oxides

The influence of synthesis conditions and Mg²⁺, Co²⁺, and Zn²⁺ admixtures on the formation of lamellar, cubic, and hexagonal mesophases was studied. After calcining at 653 K in an argon flow, the mesophases transformed into mesoporous materials with D _pore = 27–80 Å, V _pore = 0.10–0.30 cm³/g, and s _BET = 80–200 m²g. Nanotubes based on mesostructural lamellar vanadium oxide with inside diameters of from 100 to 500 Å were obtained in the presence of several amines as templates.     

Electrometric study of uranyl(II) and beryllium(II) complexes of 2,2′-dimercapto diethyl ether

Complexation of uranyl(II) and beryllium(II) ions with 2,2′-dimercaptodiethyl ether has been studied in 40% ethanolic media by potentiometric and conductometric titration techniques revealing the formation of an 1∶1 complex in either case. The stability constants of the complexes have been determined at ionic strength μ=0.1M (NaClO₄) by applyingCalvin andMelchior's extension ofBjerrum's method. LogK _stab values are found to be 12.60, 11.96 at 25 °C and 12.55, 11.90 at 35 °C respectively. The values of ΔG, ΔH and ΔS for the complexation reactions determined at 25 °C are also reported.     

The state of Cu2+ ions in concentrated aqueous ammonia solutions of copper nitrate

Stabilization of Cu²⁺ ions in concentrated aqueous ammonia solutions of copper nitrate in a wide range of ammonium ion concentrations has been studied by EPR and electronic absorption spectroscopy. Three types of Cu²⁺ associates with different types of orbital ordering have been identified. The ammonium ion concentration in a solution has a decisive effect on the type of orbital ordering of Cu²⁺ ions in associates. In all cases, Cu²⁺ ordering in associates is caused by the existence of bridging OH groups in the axial and equatorial positions of [Cu(NH₃) _n (H₂O)_{6 ? n} ]²⁺ complexes (n < 6). At a high concentration of ammonium ions, weakly bound associates of tetramminecopper with the $d_{x^2 - y^2 }$ ground state are formed. In solutions with low ammonium concentrations, bulky associates with the $d_{y^2 }$ and $d_{x^2 - z^2 }$ ground states and associates of Cu²⁺ ions with the $d_{x^2 - y^2 }$ ground state with hydroxyl groups in the equatorial plane and axial water molecules are formed.     

Theoretical investigations on nonlinear optical and spectroscopic properties of 6-(3,3,4,4,4-pentafluoro-2-hydroxy-1-butenyl)-2,4-pyrimidinedione: An efficient NLO material

In this study, quantum chemical calculations of geometric parameters, conformational, natural bond orbital (NBO) and nonlinear optical (NLO) properties, vibrational frequencies, ¹H and ¹³C NMR chemical shifts of the title molecule [C₉H₇F₅N₂O₃] in the ground state have been calculated with the help of Density Functional Theory (DFT-B3LYP/6-311++G(d,p)) and Hartree-Fock (HF/6-311++G(d,p)) methods. The optimized geometric parameters, vibrational frequencies, ¹H and ¹³C NMR chemical shifts values are compared with experimental values of the investigated molecules. Comparison between experimental and theoretical results showed that B3LYP/6-311++G(d,p) method is able to provide more satisfactory results. In order to understand this phenomenon in the context of molecular orbital picture, we examined the molecular frontier orbital energies (HOMO, HOMO-1, LUMO, and LUMO + 1), the energy difference (ΔE) between E _HOMO and E _LUMO, electronegativity (χ), hardness (η), softness (S) calculated by HF/6-311++G(d,p) and B3LYP/6-311++G(d,p) levels. The molecular surfaces, Mulliken, NBO, and Atomic polar tensor (APT) charges of the investigated molecule have also been calculated by using the same methods.     

Synthesis and characterization of some new Cd(II) and Zn(II) macrocyclic Schiff base complexes derived from cyclocondensation of three new linear aromatic (N4) amines and 2,6-diacetylpyridine. Crystal structure and biological activity studies

Six new Cd(II) and Zn(II) macrocyclic Schiff base complexes from cyclocondensation of 2,6-diacetylpyridine and three different liner aromatic amines have been investigated. The resulting ligands, L¹ and L² are 17- and L³ 18-membered pentaaza macrocycles. The complexes have been characterized by a variety of methods such as IR, elemental analysis, EI-Mass and conductivity measurements and in the case of cadmium complex by ¹H and ¹³C NMR spectroscopy. The crystal structure of [CdL¹(CH₃OH)](ClO₄)₂ has been determined. In this complex, the Cd(II) ion is coordinated to five nitrogen donor atoms of the ligand and one oxygen atom from methanol in a N₅O environment. The geometry around the cadmium can be better described as in a slightly distorted pentagonal-pyramidal. The synthesized compounds have antibacterial activity against the three gram-positive bacteria: S. aureus, B. cereus and C. xerosis, and also against the three gram-negative bacteria: E. coli, K. pneumoniae and P. vulgaris. The results show that the antibacterial activity of cadmium complexes is greater than that of zinc complexes.     

Structure of two new compounds of fluoroquinolone antibiotics with mineral acids

New compounds of sparfloxacin (C₁₉H₂₂F₂N₄O₃, SfH) and levofloxacin (C₁₈H₂₀FN₃O₄, LevoH) with mineral acids, namely, sparfloxacinium bromide (SfH · HBr, I) and levofloxacindium diperchlorate (LevoH · 2HClO₄, II), have been synthesized and characterized by X-ray diffraction. Crystallographic data are a = 7.7151(7) Å, b = 26.109(3) Å, с = 10.008(1) Å, β = 103.556(1)°, V = 1959.7(3) ų, space group P2₁/n, Z = 4 for I and a = 9.727(6) Å, b = 20.440(12) Å, с = 12.286(7) Å, β = 104.327(8)°, V = 2367(2)ų, space group P2₁, Z = 4 for II. The structures of these compounds are stabilized by intra- and intermolecular hydrogen bonds and π–π interaction between SfH₂⁺ or LevoH₃²⁺ ions.     

Synthesis and recognition properties of α-d-glucose-based fluorescent crown ethers incorporating an acridine unit

Two new chiral glucopyranoside-based crown ethers incorporating acridine fluorescent signalling units, 15-membered ligand 1 and 21-membered ligand 2 were synthesized. Their complexation properties toward alkali and alkali earth metal ions, and their enantioselectivity towards chiral ammonium salts were studied by absorption and fluorescence spectroscopic experiments. Macrocycle 1 formed 1:1 complexes with all the metal ions selected and the stability constants were low (lg K < 2.3). The cavity-size of 2 allowed only the complexaton of organic ammonium ions. Crown 2 showed chiral discrimination in case of all the four ammonium salts used as model guest compounds; the highest enantioselectivity (K(R)/K(S) ~3) was observed for the enantiomers of phenylethyl ammonium perchlorate. Ligand 2 forms much more stable complexes with metal ions; the highest stability constant was obtained for the Ca²⁺ complex (lg K = 6.15). The coordination of metal ions by ligand 2 was accompanied by marked fluorescence enhancement, whereas the binding of ammonium ions by the same species resulted in significant fluorescence quenching.     

Synthesis and crystal structure of nickel(II) dinitrate molecular complex with 3,5-lutidine

Complex [Ni(NO₃)₂(3,5-lutidine)₃] (3,5-lutidine, 3,5-Lut-C₇H₉N) was synthesized, and its crystal structure was determined. Complex crystals are monoclinic: space group Cc, a = 14.445(1) Å, b = 10.024(1) Å, c = 17.607(1) Å, β = 108.96(1)°, V = 2411(1) ų, ρ_calcd = 2.389 g/cm³, Z = 4. The structure is built of discrete neutral complexes [Ni(3,5-Lut)₃(NO₃)₂]. The coordination sphere of Ni²⁺ ions is a disordered octahedron, which consists of three crystallographically nonequivalent lutidine ligands (Ni-N, 2.059–2.124 Å) and two oxygen ions of the two nitrate ions (Ni-O, 2.047–2.258 Å).     

Cobalt(II) hexaiododimercurate(II) complex with ε-caprolactam: Synthesis and crystal structure

The conditions of synthesis of a new binary complex salt [Co(Cpl)₆][Hg₂I₆] (Cpl is ε-caprolactam ε-C₆H₁₁NO) have been developed, and its structure has been characterized. The salt crystallizes in triclinic system, space group \(P\bar 1\), a = 10.1078(4) Å, b = 12.2680(5) Å, c = 13.0782(5) Å, α = 62.872(2)°, β = 72.394(2)°, γ = 76.834(2)°, V = 1367.98(9) ų, Z = 1, and ρ_calc = 2.297 g/cm³. The structure is insular and consists of isolated ions.     

Synthesis and crystal structure of (NH<Subscript>4</Subscript>)(CN<Subscript>3</Subscript>H<Subscript>6</Subscript>)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of (NH₄)(CN₃H₆)[UO₂(SeO₃)₂] (I) are synthesized and studied by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with the unit cell parameters: a = 7.0051(2) Å, b = 9.4234(3) Å, c = 9.5408(3) Å, α = 88.727(1)°, β = 70.565(1)°, γ= 77.034(1)°, space group P ₁, Z = 2, R = 0.0224. The main structural units of crystals I are the [UO₂(SeO₃)₂]^2? chains of the crystal-chemical group AB²B₁₁ (A = UO ₂ ²⁺ , B₂= SeO₃ ^2?, B₁₁= SeO₃ ^2?) of the uranyl complexes. The uranium-containing complexes are joined into a three-dimensional framework by the ammonium and guanidinium ions and a system of hydrogen bonds.     

Application of solvation excess concept to solutions of 3 : 1 and 1 : 3 electrolytes

Data on water activity in solutions of a series of 3 : 1 and 1 : 3 electrolytes [AlCl₃, Al(NO₃)₃, LaCl₃, La(NO₃)₃, H₃PO₄, NaH₂PO₄] have been generalized in the frame of solvation excesses concept. Solvation excess reflects the distribution of the selected structural elements (ions or solvent particles) in the solution. The computed values have demonstrated the opposite contributions of ion association and hydration of ions and ion associates. Solvation excess concept allows determination of water molecules fraction constituting the excess at ions and their associates. The comparison of results obtained with different choice of model structural units has shown the electrolyte concentration ranges of validity of the respective models.     

Synthesis and properties of (VO)<Subscript>0.09</Subscript>V<Subscript>0.18</Subscript>Mo<Subscript>0.82</Subscript>O<Subscript>3</Subscript> · 0.54H<Subscript>2</Subscript>O microrods

The (VO)_0.09V_0.18Mo_0.82O₃ · 0.54H₂O microrods of hexagonal symmetry system with the unit cell parameters a = 10.586 Å and c = 3.698 Å were obtained for the first time under hydrothermal conditions (T = 160°C, τ = 30?50 h). Particles were 1–2 μm in diameter and up to 45 μm in length. The compound is thermally stable up to 469°C. The core-electron Mo3d, V2p, and O1s and valence-band X-ray photoelectron spectra and IR spectra of the samples were studied. The molybdenum atoms in the complex oxide have the oxidation state Mo⁶⁺. The vanadium atoms introduced into the h-MoO₃ lattice in molybdenum positions have the oxidation state V⁵⁺. Approximately one-third of vanadium atoms as vanadyl ions (VO)²⁺ are located in the channels of h-MoO₃ lattice, thus stabilizing the latter.     

Synthesis and structure of (NH4)2[(UO2)2(C2O4)(CH3COO)4] · 2H2O

Single crystals of (NH₄)₂[(UO₂)₂C₂O₄(CH₃COO)₄] · 2H₂O have been synthesized and studied. The compound crystallizes in the orthorhombic system with the unit cell parameters a = 6.9225(14) Å, b = 12.327(3) Å, c = 14.619(3) Å, space group Immm, Z = 2, and V = 1247.6(5) ų. The main structural units of the crystals are the isle binuclear groups [(UO₂)₂C₂O₄(CH₃COO)₄]^2? belonging to the crystal-chemical group A₂K⁰²B ₄ ⁰¹ (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B⁰¹ = CH₃COO^?) of the uranyl complexes. The uranium-containing groups are linked into a three-dimensional framework due to electrostatic interaction with the ammonium cations and through a system of hydrogen bonds involving atoms of the water molecules, oxalate and acetate ions, and ammonium and uranyl cations.