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UV light photolysis of
dichloroacetyl chloride (CHCl2COCl) has been investigated by
infrared spectroscopy in cryogenic Ar, Kr, Xe, and O2 matrices. The formation of CHCl3 and CO was found to be the dominant
process over the ketene formation. The C-C bond cleaved products CHCl2 and COCl were also observed. As the
number of the chlorine atom substitution to methyl group of acetyl chloride
increased, the C-C bond cleaved product yield in the triplet state increased,
which can be attributed to an internal heavy-atom effect where the intersystem
crossing rate was enhanced.
The addition and abstraction reactions of OH radical with benzoate anion are investigated by density functional theory calculations that include solvent effects using UB3LYP, UCAM-B3LYP, UmPW1PW91 and UM06-2X functionals with the 6-311++G(2d,2p) basis set. Geometry optimizations of the reactants, products and transition state species are performed for the possible reaction paths. For the addition reactions, those targeting the ipso-, ortho-, meta- and para-carbons are predicted to be exoergic. The H-atom abstraction reactions from ortho, meta and para positions are also predicted to be exoergic. On the basis of the rate constants calculated by means of the transition state theory, the H-atom abstraction reaction from the ortho position is determined to be the favored path followed by the ortho OH addition reaction.
This study examines how complex linguistic structures are acquired in child English as a second language. The spontaneous speech producing by a Japanese primary school child, learning English in a naturalistic environment, was audio-recorded regularly over two years and the development of complex syntactic structures containing subordinate clauses was compared with the acquisition of other English morphosyntactic structures as represented within Processability Theory (PT) (Pienemann, 1998; Pienemann, Di Biase, & Kawaguchi, 2005). Although PT predicts that subordination is acquired at the highest stage in processability hierarchy, the results in this longitudinal study show that some of the subordinate constructions emerge at earlier stages in child ESL acquisition.