Multifunctional acid formation from the gas-phase ozonolysis of beta-pinene

The gas-phase ozonolysis of beta-pinene was studied in static chamber experiments, using gas chromatography coupled to mass spectrometric and flame ionisation detection to separate and detect products. A range of multifunctional organic acids-including pinic acid, norpinic acid, pinalic-3-acid, pinalic-4-acid, norpinalic acid and OH-pinalic acid-were identified in the condensed phase after derivatisation. Formation yields for these products under systematically varying reaction conditions (by adding different OH radical scavengers and Criegee intermediate scavengers) were investigated and compared with those observed from alpha-pinene ozonolysis, allowing detailed information on product formation mechanisms to be elucidated. In addition, branching ratios for the initial steps of the reaction were inferred from quantitative measurements of primary carbonyl formation. Atmospheric implications of this work are discussed.     

Pseudohalides of boron subphthalocyanine

The synthesis and study of a series of pseudohalides of boron subphthalocyanine (BsubPc) are reported. Each pseudohalide has been compared to the more common chloride and bromide of BsubPc, and we have found that most react slower under standard phenoxylation and hydrolysis conditions. Three pseudohalides (TsO-BsubPc, MsO-BsubPc, and BsO-BsubPc) do not hydrolyze at all even after prolonged periods of time in the presence of water. Single crystals of TsO-, MsO-, and ClsO-BsubPc were obtained, and their structures were unambiguously determined.     

Reactions of hydroxyl radicals with alkenes in low-temperature matrices

The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H2O2, and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices--methanol, ethanol, ethanol-d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol (iso-butyl alcohol), 2-methylpropan-2-ol (tert-butyl alcohol), 2-methylbutan-2-ol (tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows--from ethene, 2-hydroxyethyl radical: from cis- or trans-but-2-ene. 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene. 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene (iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2-hydroxyethyl radical has been backed up by experiments utilising isotopic substitution with 13C and D (2H). The other radicals have been identified with varying degrees of certainty. Those radicals, which are observed at the highest concentration and which are, therefore, characterised more certainly are--2-hydroxyethyl (1), from ethene: 1-methyl-2-hydroxypropyl (2), from cis- and trans-but-2-ene; 1-methyl-2-hydroxyethyl (3), from propene; 1-hydroxymethylpropyl (5), from but-1-ene; and 1,1- dimethyl-2-hydroxyethyl (8), from 2-methylpropene.     

Infrared diode laser spectroscopy of jet-cooled NiCO, Ni(CO)3 (13CO), and Ni(CO3(C 18O)

Gas phase infrared spectroscopic investigations of the CO vibration of jet-cooled NiCO, Ni(CO)3(13CO), and Ni(CO)3(C18O) are reported. The spectra were obtained using a recently assembled pulsed-discharge slit-jet IR diode laser spectrometer. The rotationally resolved spectrum of NiCO was collected as it was formed in the discharge, while the spectra of Ni(CO)3(13CO) and Ni(CO)3(C18O) were recorded as they were destroyed. For NiCO, band origins of 2010.692 89(34) and 2010.645 28(23) cm(-1) were measured, along with values of B0=0.151 094(7) and 0.149 597(6) cm(-1) and B(1)=0.150 244(7) and 0.148 742(6) cm(-1) for 58NiCO and 60NiCO, respectively. The B0 values for these isotopologs were used to determine the two bond lengths in NiCO, giving r0 (Ni-C)=1.641(40) A and r0 (C-O)=1.193(53) A, in agreement with recent microwave measurements. The constants determined for Ni(CO)3(13CO) were upsilon0=2022.075 753(95) cm(-1), B"=0.034 736(2) cm(-1), and B'=0.034 688(2) cm(-1). For Ni(CO)3(C18O), upsilon0=2021.936 83(18) cm(-1), B"=0.033 764(4) cm(-1), and B'=0.033 710(4) cm(-1) were obtained. From these rotational constants, bond lengths of r0 (Ni-C)=1.839+/-0.007 A and r0 (C-O)=1.121+/-0.010 A were obtained. These values are discussed in relation to the bond lengths measured by electron and x-ray diffraction methods.     

Axial radiation force exerted by general non-diffracting beams

The axial radiation force exerted by a general non-diffracting beam on an object of arbitrary shape in lossless medium is analyzed. The object may be on or off the beam's axis. The analysis is based on the plane-wave representation of the beam using an azimuthal function and conical angle. The analytical expression relates the force to axial projections of the extracted and scattered momentum. Using an extended optical theorem, the extinction is related to the scattering at the forward direction of the beam's plane wave components. The axial force is expressed using the scattering amplitude and known angular functions.