The crystal structure of Rb2CdCl4 in para- and ferroelastic phases

Abstract

The crystal structure of Rb₂CdCl₄ has been studied by X-ray diffraction at 295 and 160 K in the initial phase D ¹⁷ _4h as well as at 105 K in the ferroelastic phase. It was found that the phase transition D ¹⁷ _4h ? D ¹⁰ _2h takes place instead of D ¹⁷ _4h ? D ¹⁸ _2h as proposed earlier. The first of the transitions corresponds to unequal and the second to equal Φ-tilts of CdCl₆-octahedra around the a and b axes of the tetragonal unit cell.     

Theoretical study of the A 3 0 + ← X 1 0 + and B 3 1 ← X 1 0 + transitions in the Cd-rare gas van der Waals molecules

Excitation spectra arising from A ³ 0 ⁺ ← X ¹ 0 ⁺ and B ³ 1 ← X ¹ 0 ⁺ electronic transitions in the Cd-rare gas (RG) van der Waals molecules are calculated using newly obtained theoretical potential curves for these species. In the molecular structure calculations, Cd²⁰⁺ and RG⁸⁺ cores are simulated by energy-consistent pseudopotentials which also account for scalar-relativistic effects and spin-orbit (SO) interaction within the valence shell. Potential energies in the Λ S coupling scheme have been obtained by means of ab initio complete-active-space multiconfiguration self consistent-field (CASSCF)/complete-active-space multireference second-order perturbation theory (CASPT2) calculations with a total 28 correlated electrons, while the SO matrix has been computed in a reduced CI space restricted to the CASSCF level. The final Ω potential curves are obtained by diagonalization of the modified SO matrix (its diagonal elements before diagonalization substituted for the corresponding CASPT2 eigen-energies). The spectroscopic parameters for the ground and several excited states of the Cd-RG complexes deduced from the calculated potential curves are in quite reasonable agreement with available experimental data. In addition, the radial Schr?dinger equation for nuclear motion was solved numerically with the calculated potentials to evaluate the corresponding vibrational levels and radial wavefunctions. The latter have been used in the calculation of the appropriate Franck-Condon factors to yield information on relative intensities of the vibrational bands of the Cd-RG complexes. The theoretical vibrational progressions are discussed in the context of experimental spectra. Received 10 August 2000 and Received in final form 7 November 2000     

High resolution laser spectroscopy of NaAr: Improved interaction potential for the ground state

The absorption spectrum of NaAr has been investigated with high resolution using a supersonic beam of molecules and a tunable dye laser. About 3 300 absorption lines due to the transition A ² Π ← X and B ² Σ ← X have been observed. In addition, we observed the spectral distribution of the fluorescence for a particular absorption line. From all experimental data the X ² Σ ⁺ interaction potential has been deduced in a fully quantum-mechanical method of approach. The potential is given in terms of an analytical Hartree-Fock-Dispersion function. For the equilibrium parameters of the X state we get R _e = 5.01(1) ? and D _e = 41.6(2) cm ^-1 . Received 28 August 2002 / Received in final form 15 October 2002 Published online 17 December 2002 RID="a" ID="a"Now at Knick Elektronische Messger?te, Beuckestr. 22, 14163 Berlin, Germany. RID="b" ID="b"e-mail: dz@kalium.physik.tu-berlin.de     

Conformational Analysis of 4,4-Dimethylheptane

Abstract

Infrared and Raman spectra were obtained for 4,4-dimethylheptane and were interpreted with the aid of normal coordinate calculations. It was shown that this compound exists in three conformations. Force constant values transferred from dimethylpentanes resulted in an overall average difference between observed and calculated wavenumbers of 4.5 cm^?1 for the three conformers.     

The Electronic Absorption Spectrum of Hafnium Monochloride

Abstract

Intracavity laser spectroscopy has been applied for investigation of absorption spectrum of HfCl molecule. In the region 560–700 nm 59 bands have been obtained. Rotational structure analysis of 0–0 band indicated that Hund's case (c) of angular moment coupling applied to this molecule. The molecular constants (cm^?1) calculated for upper and ground electronic states are: ω′ = 353.05 cm^?1, ω″ = 379.65 cm^?1, B′=0.21486 cm^?1 B″ = 0.21801 cm^?1.     

PreCon: A Fully Automated Interface for the Pre-Gc Concentration of Trace Gases on Air for Isotopic Analysis

Abstract

For the high precision isotope analysis of atmospheric trace gases a computer controlled concentration interface has been developed. From small air samples it collects either N₂O or CO₂ derived from CH₄ at their respective concentrations (0.3 ppm for N₂O, 1.7 ppm for CH₄) into a small diameter cold trap (?196°C) and interfaces via GC and open split to an isotope ratio mass spectrometer (Finnigan MAT 252) for on-line isotope evaluation. External reproducibilities for repeated measurements of 100 ml air samples from the same source of < 0.2° (δ-notation) have been achieved for ¹³C/¹²C from CH₄ and for ¹⁵N/¹⁴N and ¹⁸O/¹⁶O from N₂O. The precision is adequate to monitor the isotopic changes in these gases during a day's course.     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Vibrational Spectrometry Strategies for Quality Control of Procymidone in Pesticide Formulations

Abstract

Two vibrational spectrometry–based methodologies were developed for procymidone determination in wettable powdered pesticide formulations. The Fourier‐transform infrared (FTIR) procedure was based on the selective extraction of procymidone by chloroform and determination by peak area measurement between 1451 and 1441 cm^?1, using a baseline correction established between 1490 and 1410 cm^?1, and a precision of 0.4% and a limit of detection of 0.01% w/w procymidone for a sample mass of 25 mg were obtained. For FT‐Raman determination, the selected conditions were peak area measurement between 1005 and 995 cm^?1 Raman shift, with a baseline correction fixed between 1030 and 947 cm^?1, and a relative standard deviation of 1% and a limit of detection of 0.8% procymidone in the original sample were obtained. The sample frequency for FTIR determination was 30 hr^?1, lower than that for Raman with 40 hr^?1. FT‐Raman reduces to the minimum the reagent consumption and waste generation, also avoiding the sample handling and contact of the operator with the pesticide. It can be concluded that the proposed methods are appropriate for quality control in commercial pesticide formulations.     

Diode laser slit-jet spectra and analysis of the fundamental of 1-chloro-1,1-difluoroethane (HCFC-142b)

High resolution infrared spectra (0.001 cm^-1) have been measured for mixtures of 1-chloro-1,1-difluoroethane in Ne, expanded in a supersonic planar jet. The ν ₇ fundamental has been analyzed for both isotopic species, CH₃CF₂ ³⁵Cl and CH₃CF₂ ³⁷Cl. A weak b-type component has been observed for the first time. Received 20 May 2002 / Received in final form 10 July 2002 Published online 24 September 2002 RID="a" ID="a"Also: Dipartimento di Scienze Fisiche Universitá di Napoli “Federico II” Complesso Universitario di M.S. Angelo, 80126 Napoli, Italy. e-mail: m.snels@isac.cnr.it     

Vibrational Spectra and Normal Coordinate Analysis for an Imidazole Bridged Copper,Zinc Binuclear Complex

Abstract

The normal coordinate analysis of a model compound for Cu, Zn-SOD: [(dtma)CuImZn(dtma)]CIO₄ · 2.5H₂O (where dtma = 4-diethylenetriamineacctate; Im = imidazolate) has been carried out by using a Urey-Bradley force field. According to the molecular structure, 240 internal coordinates were established and 174 theoretical vibrational frequencies were calculated. Due to introducing an appropriate set of internal coordinates and force constants in the course of calculation, the calculated frequencies agree well with the observed values, with the average difference 4.40cm^?1 and the maximum deviation 24.2cm^?1 between them, although the structure of the title compound is complicated. Some structural and spectral properties are here discussed.     

Quantitative Determination of Reactive Species in Alkali Halide Disks

Abstract

As part of an infrared investigation of the kinetics of the reactions of KMnO₄ in a KI disk and of KIO₄ in a KI disk, the stoichiometry of the two reactions was needed. A previous study¹ has shown that MnO₄ ^? reacts in a KI matrix to produce IO₄ ^? (which then reacts further to form IO₃ ^?) and MnO₂. Iodate ion is the only observable product in the reaction of IO₄ ^? in a KI matrix¹. The infrared absorption at 740cm^?1, which is due to the presence of IO₃ ^?, was found to obey the Beer-Lambert Law. However, calibration curves for KMnO₄ in KI and for KIO₄ in KI could not be obtained because both species reacted with the dispersing medium during the preparation of the disk¹. It was also observed that no immediate reaction occurred when KBr or KC1 disks containing KMnO₄, or KIO₄ were prepared. Thus, an extrapolation method was sought which would permit the estimation of calibration curves for the reactive species.     

Optimization of Pretreatment Method for Alkylmercuries Speciation in Coal by High‐Performance Liquid Chromatography Coupled with UV‐Digestion Cold Vapor Atomic Fluorescence Spectrometry

Abstract

Exhaustive extraction of analytes in their original chemical forms from samples with complex matrices is a pivotal step for speciation analysis. Herein we propose a pretreatment method for extracting and preconcentrating methylmercury and ethylmercury from coal samples by using KBr–H₂SO₄/CuSO₄–C₆H₅CH₃–Na₂S₂O₃ system. The extraction conditions, including the volume of the organic phase and the extraction time, were optimized in detail. Speciation analysis of alkylmercuries was carried out by high‐performance liquid chromatography online coupled with UV‐digestion and cold vapor atomic fluorescence spectrometry. The detection limits were 0.6 ng mL^?1 for methylmercury and 1 ng mL^?1 for ethylmercury, respectively. The recoveries of methylmercury and ethylmercury spiked in a sample were 84% and 82%, respectively. The method was applied successfully to analysis of alkylmercuries in four coal samples collected from northeast China.     

Exact Analysis of Level-Crossing Statistics for (d+1)-Dimensional Fluctuating Surfaces

We carry out an exact analysis of the average frequency ν⁺ _αxi in the direction x _i of positiveslope crossing of a given level α such that, h(x, t) − = α, of growing surfaces in spatial dimension d. Here, h(x, t) is the surface height at time t, and is its mean value. We analyze the problem when the surface growth dynamics is governed by the Kardar-Parisi-Zhang (KPZ) equation without surface tension, in the time regime prior to appearance of cusp singularities (sharp valleys), as well as in the random deposition (RD) model. The total number N ⁺ of such level-crossings with positive slope in all the directions is then shown to scale with time as t ^d/2 for both the KPZ equation and the RD model. PACS number(s): 52.75.Rx, 68.35.Ct     

Luminescence characteristics of ultraviolet upconversion from Er 3 + :YAG crystal by Ar + laser (488 nm) excitation

Ultraviolet and violet upconversion signals at 271 nm, 317 nm, 381 nm and 407 nm were observed when an erbium-doped YAG crystal was pumped by an Ar⁺ laser (488 nm). The dependence of intensity of luminescence emitting from the ⁴S _3/2 state and the ²P _3/2 state on pump power (I) was experimentally investigated. Changes from I¹ down to I ^1/2 for the ⁴S _3/2 state and from I² down to I¹ for the ²P _3/2 state were observed. The upconversion mechanism was discussed by means of the rate equations. It appears that energy-transfer upconversion (ETU) is a dominant process for the Er³⁺:YAG crystal used in our experiment. Received 20 March 2001 and Received in final form 11 July 2001     

Rotational Analysis of the 383.8 nm Band of the GeBr Molecule

Abstract

The 383.8 nm band of the GeBr molecule, recorded at high resolution, has been rotationally analyzed. Rotational constants of the upper and lower states have been determined from lines of six, main isotopic molecules of GeBr. The band has been proposed to be assigned as the ⁴σ^??X²π_3/2 0–0 transition.     

Fluorescence Study of the Relaxation Process in Excited Hetarylthiazole Cations

The absorption and fluorescence spectra of five cations protonated at the quinolyl nitrogen atom (IH⁺–VH⁺) and one ethylated (IEt⁺) cation were investigated. For these compounds (except VH⁺) both an anomalously large fluorescence Stokes shift (up to 238 nm) and a large short-wavelength fluorescence shift (up to 145 nm) at decreasing temperatures (down to 77 K) were observed. This is not the case for unprotonated molecules. The ground-state conjugation between quinolyl and another molecular fragment was found for II, IH⁺, IIH⁺, and IEt⁺. The relaxation process of excited cations is medium viscosity and temperature dependent. The experimental results are explained in terms of excited-state structural relaxation.     

Isotope dependent predissociation in the C 1 Σ + , v =0 and v =1 states of CO

Rotationally resolved spectral lines in the C - X (1, 0) band of carbon monoxide are investigated under high resolution using a coherent vacuum ultraviolet laser source, continuously tunable near 107 nm. Transition frequencies are determined by calibrating against a reference standard of iodine lines, recorded with saturation spectroscopy in the visible range, yielding an absolute accuracy of 0.003 cm^-1 in the vacuum ultraviolet. Improved molecular constants for the excited state are derived and no effects of perturbation are found at the present level of accuracy. Line broadening measurements result in information on the excited state lifetime of the C ¹ Σ ⁺ , v = 1 state for five natural isotopomers of carbon monoxide: τ( ¹² C ¹⁷ O ) = 280 ps, τ( ¹² C ¹⁸ O ) = 210 ps, τ( ¹³ C ¹⁶ O ) = 295 ps, τ( ¹³ C ¹⁷ O ) = 160 ps, and τ( ¹³ C ¹⁸ O ) = 150 ps. Within the accuracy of the present measurements no effects of J-dependent lifetimes were observed, for neither of the isotopomers. In addition direct time domain measurements of the lifetime of the C ¹ Σ ⁺ , v = 0 and v = 1 states of the main isotopomer are performed in a pump-probe experiment using a picosecond VUV-laser, yielding τ( ¹² C ¹⁶ O ) = 1780 ps for v = 0 and τ( ¹² C ¹⁶ O ) = 625 ps for v = 1. For C ¹ Σ ⁺ , v = 0 in ¹²C¹⁶O and ¹³C¹⁶O the same lifetime is found; this lifetime matches experimental values of the oscillator strength and hence supports previous results showing pure radiative decay in this state; the error margins however do not exclude some low level of predissociation. The measurements indicate that the C ¹ Σ ⁺ , v = 0 state of the ¹³C¹⁸O isotopomer is predissociated with an estimated yield of 17% (i.e. above the level of predissociation for ¹²C¹⁶O.) From the combined data predissociation yields upon excitation of the C ¹ Σ ⁺ , v = 1 state are derived, lying in the range 0.84-0.91 for the five less abundant isotopomers; for the main ¹²C¹⁶O isotopomer a strongly deviating predissociation yield of 0.65 is deduced. Received 21 December 2000 and Received in final form 26 March 2001     

Kinetic of Copper(III)/(II) Tetraglycine Reactions with Sulfite. Analytical Potentialities

Abstract

The oxidation of Cu(II)/tetraglycine complex in borate buffer (pH=9.2) in aqueous medium, by dissolved oxygen is strongly accelerated by S(IV). The reaction is adequate for S(IV) determination as the concentration of (Cu(H_-3G₄)]^? formed is proportional to SO₃2- concentration. The [Cu(H_-3G₄)]^? presents a maximum absorbance at 365 nm (? = 7400 mol^?1.L.cm^?1) and it was followed spectrophotometrically by flow injection analysis procedure. The detection limit was 7×10^?6 mol.L^?1 and the linear regression showed a standard deviation of 0.02% (n=5). Kinetics studies showed the catalytic effect of some transition metal ions, “which can be present in environmental samples, in the oxidation of S(IV). The pseudo-first-order rate constants were determined in the presence of formaldehyde.