(1)Prediction of phenoxyperoxy (C6H5OOO) stability (2)Theoretical study of 1,2-butadiene + Si(3P) reaction

• Main Authors: Chun-Ta Hsiao, 蕭群達
• Other Authors: Hsiu-Hwa Chang
• Format: Others
• Language: en_US
• Published: 2018
• Online Access: http://ndltd.ncl.edu.tw/handle/srh22f

碩士 === 國立東華大學 === 化學系 === 106 === (1) In this thesis, we calculated the energies of the molecule phenoxyperoxy (C6H5OOO) and predicted the probable structures. Para-C6H5O3 is slightly lower than C6H5O + O2, other geometries cycle- C6H5O3, v- C6H5O3, ortho- C6H5O3, are still in high energy, and the structure o2-C6H5O3 is difficult to considered to be the reasonable molecule because of long distance in O atom on the benzene to oxygen group. Compare with hydridotrioxygen (HOOO), Probable bulky benzene hinders the approach of O2 group approaching. (2) Through optimized the structure by B3LYP and estimated the CBS energy by coupled cluster theory with B3LYP/cc-pVTZ zero point correction, for minimum energy crossing point was calculated by MCSCF with MOLPRO program so that we can predicted possible complexes, intermediates, products and path way which result from cross beam experiments. Based on our study of 1,2-butadiene + Si(3P) collision reaction, the radical triplet silicon atom was add onto 1,2-butadiene. The previous process are highly similar as the triplet carbon atom was add onto dimethylacetylene, the reactant tend to form a triplet ring shape complexes first (3c1 through intersystem crossing we got 1c1) and ring was opened to obtain linear intermediate (1i1, 1i1’, 1i6), but we still not found any reasonable path way to get product in this case.