(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.

outline
Abstract I
Chapter1. Prediction of phenoxyperoxy (C6H5OOO) stability 1
1.Introduction 1
2.Theoretical methods 1
2.1 Anharmonicity 3
3.Result 3
4.Discussion 4
5.Reference 5
Chapter2. Theoretical study of 1,2-butadiene + Si (3P) reaction 27
1.Introduction 27
2.Theoretical methods 28
2.1 Minimum energy crossing point 30
2.3 RRKM theory for rate constant calculations 30
2.2 Variational RRKM rate constant calculations 30
3.Result 31
4.Discussion 33
5.Reference 34

Table 1. 10
Table 2. 13
Table 3.. 14
Table 4.. 15
Table 5. 16
Table 6. 65
Table 7.. 66

Figure 1 9
Figure 2 12
Figure 3 38
Figure 4 39
Figure 5 42
Figure 6 45
Figure 7 51
Figure 8 52
Figure 9 53
Figure 10 54
Figure 11 55

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