Detection of chlorinated hydrocarbons via Laser-atomization/Laser-induced fluorescence

Chlorinated hydrocarbons (CHC), photodissociated at 193 nm, are detected with high sensitivity by observing the atomic chlorine fragment via laser-induced fluorescence (LIF). Photofragment emission spectra from CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄, C₂HCl₃, and C₂Cl₄ demonstrate that photofragment fluorescence and chemiluminescence are negligible in the region 700–800 nm where the 3p ⁴4p ⁴ S ⁰ 3p ⁴4s ⁴ P fluorescence from atomic chlorine is detected. There is also negligible interference for photodissociation in Ar, N₂, and air bath gases. Total CHC can be readily detected in air flows at mixing fractions less than 20 ppb and averaging times less than 1 minute. Techniques for considerable improvement in this detection limit are discussed.Supported by the NSF     

A Computational Study of CIONO2H+: Structure and Vibrations

Two protonated forms of chlorine nitrate, HClONO⁺ ₂ and ClONO₂H⁺, are treated ab initio by the Hartree-Fock and the second order Møller-Plesset perturbation approach with the standard 6–31G* basis set. Both minimum energy structures are planar (C ₃ symmetry) and their structural, energy, and vibrational parameters are reported. The computations conclude that the proton attacks the chlorine nitrate at its central, not end, oxygen atom. The protonation causes a considerable elongation of the central ON bond which becomes most probable place of cleavage. The dissociation should yield the neutral HOCl and NO⁺ ₂. These quantum-chemical findings well agree with the previous experimental indications.

     

A total reflection X‐ray fluorescence method for the determination of chlorine at trace levels in nuclear materials without sample dissolution

A total reflection X‐ray fluorescence (TXRF) method for the determination of chlorine at trace levels in nuclear fuel samples is described. Chlorine present in trace concentrations in nuclear fuel materials such as U₃O₈, (U,Pu)C, PuO₂ and Pu‐alloys was first separated from the solid matrix by pyrohydrolysis as HCl and was collected in 5 mM NaOH solution. This solution was analyzed for chlorine by TXRF spectrometry using Cl Kα analytical line excited by W Lα. Cobalt was used as internal standard. The precision for such chlorine determination was found to be within 27% (n = 4) when the analysis was carried out in air atmosphere. This could be improved to 8% by making TXRF measurement in flowing helium atmosphere. The results obtained from TXRF determinations were also compared with those obtained from ion chromatography (IC) and were in good agreement. The collection of distillate during pyrohydrolysis in NaOH helped in counterchecking loss of chlorine during TXRF sample preparation. The average deviation of TXRF‐determined values in helium‐purged TXRF measurements with IC determined values (as chloride) was 15% at a chlorine concentration level in the range of 1–70 µg/mL. Copyright © 2012 John Wiley & Sons, Ltd.     

A theoretical investigation of the interaction between fluorinated dimethyl ethers and molecular chlorine

Halogen bonds have received a great deal of attention in recent years. In this work, the interaction between fluorinated dimethyl ethers (n_F = 0–4) and molecular chlorine has been investigated by the theoretical methods. The two molecules are bonded together by an O···Cl?Cl halogen bond and the interaction energies calculated at the MP2/aug-cc-pVDZ level range between ?15.5 (n_F = 0) and ?6.1 (n_F = 4) kJ mol^?1. The correlations between interaction energies and proton affinity or ionisation potential of the ethers are discussed. The interaction between the molecules results in a small contraction of the CH bond of ethers and an elongation of the Cl?Cl bond. The data are analysed by a natural bond orbital analysis carried out at the wB97XD/6-311++G(d,p) level. The charge transfer from the ethers to Cl₂ is weak, ranges between 0.044 and 0.008 e and occurs mainly to the external Cl atom. The elongation of the Cl?Cl bond is related to the occupation of the σ^*(Cl?Cl) orbital and to the intermolecular hyperconjugation interaction between LP(O) and σ^*(Cl?Cl) orbitals. The interaction between the ethers and chlorine induces an enhancement of the infrared intensity and Raman scattering activity of the ν(Cl?Cl) vibration.     

Influence of external electric field on the transfer of protons in hydrogen-bonded systems

The LCAO MO self-consistent field method in combination with the 6-31** basis set is used to calculate sections of the potential energy surface for a proton in the NH₃…HCl system in the presence of an external electrostatic field. The field strength is varied in the range of 0.000 to 0.017 a. u. In the absence of the field, the potential of the proton in the isolated complex has one well, the N–Cl distance is equal to 2.92 Å, and the NH₃…H–Cl bond is a hydrogen bond. With increasing distance between the N and Cl atoms, a second well appears in the potential, with the well near the Cl atom remaining deeper. In the presence of an external electric field, with increasing its strength, the depth of the well near the N atom increases, while the height of the barrier for proton transfer from the chlorine to the nitrogen atom decreases. At a certain field strength, the well near the nitrogen atom becomes deeper than that near the chlorine atom, so the proton moves to the nitrogen, making the complex ionic. Thus, the external electric field can influence the type of chemical bond in NH₃…HCl system.     

Viscoelasticity and morphology of an organic hybrid of chlorinated polyethylene and N,N′-dicyclohexyl-2-benzothiazolyl sulfenamide

The viscoelasticity and morphology of an organic hybrid of chlorinated polyethylene (CPE) and N,N′-dicyclohexyl-2-benzothiazolyl sulfenamide (DBS) were studied by means of tensile and shear complex modulus and differential scanning calorimetry (DSC) analysis. Tensile and shear loss modulus (E″ and G″), which are shown as indexes of vibration damping performance, showed one peak corresponding to the glass transition. The peak maximum values (E″_max and G″_max)increased in proportion to DBS content ( _DBS) and the slope of E″_max against _DBS became steep above a certain DBS content, i.e. the critical DBS content ( _c). A high damping material was obtained by the addition of DBS, especially when DBS content was higher than _c. These increases in loss moduli below and above _c are caused by the interaction between CPE and DBS molecules and the friction between DBS molecules, respectively. It was found that CPE/DBS is a compatible blend at all DBS contents from the analysis of the glass transition temperature with DSC. Furthermore, the influence of chlorine content in CPE on those characteristics was investigated. Higher chlorine content led to lower _c, a decrease in E″ below _c and an increase in E″ above _c. These results are due to the increase in the number of dichloromethylene units (CCl₂), which reduces the α-hydrogen atom in CPE.     

Particular features of manifestation of energy migration toward impurity in nanoparticles of metal complexes

We measure the fluorescence quantum yields (q _fl) of complexes of Al, Sc, Y, In, Lu, and Gd with dibenzoylmethane in aqueous and isopropanol solutions at different concentration ratios of ions and dike-tone. We reveal that, for the examined solutions, qfl of complexes varies more than by two orders of magnitude under the influence of the heavy atom. It is found that a considerable decrease in q _fl and τ_fl of ligands of complexes of listed ions caused by the influence of heavy atoms weakly affects the intensity of sensitized fluorescence of Nile red and rhodamine 6G molecules introduced into nanoparticles from these complexes in aqueous solutions. The revealed result is explained by the comparability of the singlet exciton free path length and the dimension of nanoparticles under study. We show that a lower fluorescence intensity of heavy metal complexes makes it possible to decrease its contribution in the range of the cofluorescence maximum of rhodamine 6G and to monitor the occurrence of the dye in the aqueous solution down to the concentration of 0.05 nM. We show that, in nanoparticles from Eu complexes, further fluorescence quenching of dibenzoylmethane is observed, as well as the appearance of cofluorescence of rhodamine 6G, the intensity of which is comparable with its intensity in nanoparticles of other complexes. The appearance of this cofluorescence cannot be explained by the existence of S-S energy migration.     

The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

Kinetic study of the formation of N‐chloro compounds using N‐chlorosuccinimide

Second‐order rate constants were determined for the chlorination reaction of 2,2,2‐trifluoethylamine and benzylamine with N‐chlorosuccinimide at 25 °C and an ionic strength of 0.5 M. These reactions were found to be of first order in both reagents. According to the experimental results, a mechanism reaction was proposed in which a chlorine atom is transferred between both nitrogenous compounds. Kinetics studies demonstrate that the hydrolysis process of the chlorinating agent does not interfere in the chlorination process, under the experimental conditions used in the present work. Free‐energy relationships were established using the results obtained in the present work and others available in the literature for chlorination reactions with N‐chlorosuccinimide, being the pK_a range included between 5.7 and 11.22. Copyright © 2014 John Wiley & Sons, Ltd.     

Long-range interactions of the chlorine atom

The dispersion interactions of the chlorine atom ground state with atomic hydrogen and itself are computed with a matrix element tabulation derived from the box-based B-spline configuration-interaction method. The matrix element list was also used to calculate the quadrupole and octupole polarisabilities of the chlorine ground state.     

Kamlet-Taft and Catalan Studies of Some Novel Y-Shaped Imidazole Derivatives

Some novel Y-shaped imidazole derivatives were developed and characterized by NMR and mass spectral techniques. The photophysical properties of these imidazole derivatives were studied in several solvents. The Kamlet-Taft and Catalan’s solvent scales were found to be the most suitable for describing the solvatochromic shifts of the absorption and fluorescence emission. The adjusted coefficient representing the electron releasing ability or basicity of the solvent, C _β or C _SB has a negative value, suggesting that the absorption and fluorescence bands shift to lower energies with the increasing electron-donating ability of the solvent. This effect can be interpreted in terms of the stabilization of the resonance structures of the chromophore. The observed lower fluorescence quantum yield may be due to an increase in the non-radiative deactivation rate constant. This is attributed to the loss of planarity in the excited state provided by the non co-planarity of the cinnamaldehyde ring attached to C(2) atom of the imidazole ring. Such a geometrical change in the excited state leads to an important Stokes shift, reducing the reabsorption and reemission effects in the detected emission in highly concentrated solutions.     

Vacuum-ultraviolet photoionization of bromoform and its chlorine substituted counterparts during condensation with argon at 15 K: Infrared spectra of the (CHX2+)X and X−-HCX2 molecular ions

Samples of bromoform, bromoform-d and the chlorine substituted counterparts were deposited onto a 15 K cold window during simultaneous irradiation from an open microwave discharge of argon. Infrared absorptions previously assigned to daughter cations and anions showed a 2 to 10 cm^?1 dependence on the detached chlorine or bromine atom, which appears to be trapped in the same matrix cage with the molecular fragment. Spectroscopic considerations favor the (CHX₂⁺)X and X^?-HCX₂ identifications for these ionic species. Subsequent photolysis with the filtered light of a mercury arc selectively destroyed these ions and produced CX₃, CX₃⁺, and Ar_nH⁺ or Ar_nD⁺ upon rearrangement with the detached halogen atom.     

Calculation of vibrational spectra for dioxouranium monochloride monomer and dimers

Structural models were built and spectral characteristics were calculated based on ab initio calculations for the monomer and dimers of dioxouranium monochoride UO₂Cl. The calculations were carried out in the effective core potential LANL2DZ approximation for the uranium atom and all-electron basis sets using DFT methods for oxygen and chlorine atoms (B3LYP/cc-pVDZ). The monomer UO₂Cl was found to possess an equilibrium planar (close to T-shaped) configuration with C_2v symmetry. The obtained spectral characteristics were analyzed and compared with experimental data. The adequacy of the proposed models and the qualitative agreement between calculation and experiment were demonstrated.     

Sub-poissonian statistics of fluorescence photons of a single molecule

The method previously used by the author for the measurement and calculation of the distribution function w _N(T)of fluorescence photons from a single two-level atom that is continuously excited by laser light and has a unity fluorescence quantum yield is generalized to the case of a single molecule whose fluorescence quantum yield is smaller than unity and to the case of a three-level molecule whose fluorescence is blinking. The functions w _N(T) calculated for these two cases demonstrate a sub-Poissonian distribution of fluorescence photons.     

A New Relation Connecting Vibrationai Constant and Electronegativity in the Case of Diatomic Molecules

The electronegativity was defined by Pauling¹ as a measure of the power of an atom in the molecule to attract electrons to itself. This concept of electronegativity has undergone radical changes. Recent calculations of electronegativity show^2,3 that it is a complex quantity including an important atomic term depending on the charge and hybridization of the atom, and a molecular term depending on the length and the nature of the bonds in the molecule. In a molecular group of the type A-B, B is a halogen atom, say chlorine and A stands for different atoms of a subgroup of the periodic table. Since the nature of the bonds in the molecule AB and the electronegativity of halogen atom, B, is constant for a molecular group, the electronegativity, X, of atom A may be related to the dissociation energy and bond length which in its turn is related to the vibrational constant,ω_e, and the reduced mass, μ, of the molecule AB.     

The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X Σ)

The pure rotational spectrum of HZnCl (X ¹Σ⁺) has been recorded using sub-millimeter direct-absorption methods in the range of 439–540 GHz and Fourier transform microwave (FTMW) techniques from 9 to 39 GHz. This species was produced by the reaction of zinc vapor and chlorine gas with H₂ or D₂ in a d.c. glow discharge for the sub-millimeter studies. In the FTMW measurements, HZnCl was created in a discharge nozzle from Cl₂ and (CH₃)₂Zn. Between 5 and 10 rotational transitions were measured in the sub-millimeter regime for four zinc and two chlorine isotopologues; four transitions were recorded with the FTMW machine for the main isotopologue, each consisting of several chlorine hyperfine components. The data are consistent with a linear molecule and a ¹Σ⁺ ground electronic state. Rotational and chlorine quadrupole constants were established from the spectra, as well as an r_m⁽²⁾ structure. The Zn–Cl and Zn–H bond lengths were determined to be 2.0829 and 1.5050 Å, respectively; in contrast, the Zn–Cl bond distance in ZnCl is 2.1300 Å, longer by 0.050 Å. The zinc–chlorine bond distance therefore shortens with the addition of the H atom. The ³⁵Cl electric quadrupole coupling constant of eQq = −27.429 MHz found for HZnCl suggests that this molecule is primarily an ionic species with some covalent character for the Zn–Cl bond.     

A study of the molecular structure and of the barrier to methyl rotation in o-chlorotoluene partially oriented in the nematic phase

The N.M.R. spectrum of o-chlorotoluene, dissolved in the nematic phase of 4-methoxybenzylidene-4-amino-α-methylcinnamic acid n-propylester is analysed and the shape of the proton skeleton determined. The position of lowest energy of the potential barrier to methyl rotation is found to be that in which the chlorine atom is staggered to the methyl group, and the height of the barrier is of the order of 5·0 kJ mol^-1 (1200 cal/mole).     

Heusler合金Mn2NiGe磁性形状记忆效应的第一性原理预测

运用基于密度泛函理论的第一性原理,对Hg₂CuTi型Mn₂NiGe的四方变形、晶体结构、磁性、电子结构、压力响应等进行了计算.计算结果表明: 1)在由立方结构至四方结构的转变中,在c/a约为1.34处存在一个稳定的马氏体相;2)在奥氏体态和马氏体态下,Mn原子均是Mn₂NiGe总磁矩的主要贡献者,但Mn(A),Mn(B)原子磁矩的值不等且呈反平行耦合,因而Mn₂N 关键词： 第一性原理 磁性形状记忆 四方变形 马氏体相变     

Modification of the Xe 4d giant resonance by the C60 shell in molecular Xe@C60

It is demonstrated that in photoabsorption of the 4d ¹⁰ subshell of a Xe atom in molecular Xe@C₆₀, the 4d giant resonance that characterizes the isolated Xe atom is distorted significantly. The reflection of photoelectron waves by the C₆₀ shell leads to profound oscillations in the photoionization cross section such that the Xe giant resonance is transformed into four strong peaks. Similarly, the angular anisotropy parameters, both dipole and nondipole, are also modified. The method of calculation is based on the approximation of the C₆₀ shell by an infinitely thin bubble potential that leaves the sum rule for the 4d-electrons almost unaffected, but noticeably modifies the dipole polarizability of the 4d-shell. The text was submitted by the authors in English.