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81.
R. Lefbvre 《Chemical physics letters》1980,70(3):430-433
The complex rotation method is applied to the determination of widths and shifts of an harmonic oscillator predissociated by a linear potential, for when exact analytical formulas are available in the limit of small interchannel coupling. Excellent agreement is obtained. 相似文献
82.
Equilibria and kinetics for the extraction of nickel(II) and copper(II) by 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N) in seven organic solvent systems were studied in order to test the validity of several hypotheses related to the role of the solvent in equilibrium and kinetic aspects of metal chelate extraction. For the nickel—LIX 65N system, the extraction constant is essentially independent of the solvent system, whereas for the copper—LIX 65N system, the extraction constant is not independent of solvent; this indicates that while the stoichiometry of the nickel chelate remains the same in all solvents, that of copper does not. The observed rate constant for the nickel—LIX 65N extraction was found to vary inversely with the LIX 65N distribution constant as predicted from a mechanism involving slow formation of the 1:1 complex. The observed reaction rate constant for the copper—LIX 65N varied inversely with the square of the distribution constant, also in accordance with the previously postulated mechanism of the slow formation of the 2:1 copper complex. This study, therefore, unequivocally eliminates the interfacial mechanism in favor of the homogeneous chemical reaction mechanism for the extraction of metal ions by LIX 65N, as well as by other similar high-molecular-weight extractants. 相似文献
83.
The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R2UPh type and -thioureas of the R2TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments. 相似文献
84.
Ab initio calculations are presented for H2 and D2 relative Raman intensities originating from common rotational levels for both vibrational-rotational and pure rotational transitions. Factors f(J) required to correct measured intensities for molecular non-rigidity (e.g. in temperature measurements) are tabulated. The calculations are compared with literature perturbation-theory equations (significant differences at large J in vibration-rotation) and with experiment. 相似文献
85.
The ionization threshold of fluoranthene and of TMPD in n-pentane was determined by laser two-photon ionization (TPI) and found to be 4.50 ± 0.05 and 3.88 ± 0.05 eV respectively. For both molecules the TPI spectra show distinct structure due to autoionization. For fluoranthene the TPI spectrum suggests that the molecule dissociates via the first excited singlet state. 相似文献
86.
Berberine chloride (1) upon treatment with NaOAc-Ac2O yields naphthalene derivatives 4 and 5 In like fashion, 8 gives naphthalene 10; isoquinoline methiodide leads to β-naphthyl acetate; and 12 provides 14. The reaction has been extended to the 3-carbonyl pyridinium series where 3-acetylpyridine methiodide and 3-pyridinecarboxaldehyde methiodide furnish lactones 16 and 17, respectively. All these transformations proceed by initial nucleophilic attack of the acetic anhydride anion on the immonium carbon atom. 相似文献
87.
Raman and IR spectra of methylarsonic acid, CH3AsO3H2, trideuteromethylarsonic acid, CD3AsO3H2 and their anions in aqueous solution and the solid state are discussed. Some results of a general valence force field and a Urey-Bradley force field are reported. 相似文献
88.
The fluorescence decay of the tertiary aliphatic animes trimethylamine (TMA), triethylamine (TEA) and tri-n-propylamine (TPA) in the vapour phase excited between 260 and 215 nm has been shown to consist of a single, wavelength-dependent, component when the first excited state is uniquely excited, but two components when the first and second excited states are simultaneously excited. This dual exponentiality persists at pressures as low as 10 mTorr, and it is argued that the two-component decay does not arise from collisional vibrational relaxation. 相似文献
89.
The molecular structure and conformation of 2,3-dichloro-1-propene have been determined by gas-phase electron diffraction at nozzle temperatures of 24, 90 and 273°C. The molecules exist as a mixture of two conformers with the chlorine atoms anti (torsion angle ∠φ = 0°) or gauche (∠φ = 109°) to each other and with the anti form the more stable. The composition (mole fraction) of the vapor with uncertainties estimated at 2σ was found to be 0.55 (0.08), 0.49 (0.08) and 0.41 (0.10) at 24, 90 and 273°, respectively. These values correspond to an energy difference with estimated standard deviation ΔE° = E°g-E°a = 0.7 ± 0.3 kcal mol?1 and an entropy difference ΔS° = S°g-S°a = 0.6 ± 0.9 cal mol?1 K?1. Some of the diffraction results, together with spectroscopic observations, permit the evaluation of an approximate torsional potential function of the form 2V = V1 (1 - cos φ) + V2 (1 - cos 2φ) + V3 (1 - cos 3φ); the results are V1 = 4.4 ± 0.5, V2 = ?2.9 ± 0.5 and V3 = 4.8 ± 0.2, all in kcal mol?1. The results at 24°C for the distance (ra) and angle (∠α) parameters, with estimated uncertainties of 2σ, are: r(Csp2-H) = 1.098(0.020)Å, r(Csp3-H) = 1.103(0.020)Å, r(CC) = 1.334(0.009)Å, r(C-C) = 1.504(0.013)Å, r(Csp2-Cl) = 1.752(0.021)Å, r(Csp3-Cl) = 1.776(0.020)Å, ∠C-CC = 127.6(1.1)°, ∠Csp3-Csp2-Cl = 110.2(1.0), ∠Csp2-Csp3-Cl = 113.1(1.2)°, ∠H-Csp3-H = 109.5° (assumed), ∠CC-H = 120.0° (assumed) and ∠φ = 108.9(3.4)°. 相似文献
90.
A coulometric procedure has been developed by which 18 to 240 μg quantities of bromate may be determined to within 0.3 μg. The bromate is allowed to react with bromide in an acid solution and electrolytically generated cuprous copper is used for the titration. A dual platinum electrode indicator system is used in an amperometric end-point procedure 相似文献