(1) Reaction dynamics of Disilavinylidene(H2SiSi) formation. (2) Electronic properties of platinum complexes bearing normal and mesoionic NHC based pincer ligands.
| Autor: | Kang-Heng Chao, 趙康衡 |
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| Rok vydání: | 2016 |
| Druh dokumentu: | 學位論文 ; thesis |
| Popis: | 104 (1) In this thesis, we investigate the reaction of Si(3P) – SiH4(X1A1) in single collision condition. Density functional theory with functional, B3LYP and coupled cluster theory, and CCSD with cc-pVTZ basis set are used to optimize the geometries of the collision complexes, intermediates, products and transition states. The CCSD/CBS energies are then obtained. In this reaction, the intermediate 3i1 can convert to 1i1 via intersystem crossing. The minimum-energy crossing structures are predicted by CPMCSCF method with TZVPP basis set. The products observed experimentally are presumably singlet surface. The RRKM rate constants are computed to estimate product yields on singlet surface. The major product is found to be disilavinylidene (SiSiH2), an isovalent analogue of vinylidene (CCH2). (2) The molecular orbitals for the platinum complexes of mesoionic-triazol-5-ylidene and pyridine-bis-imidazol-2-ylidene with acetonitrile. We use B3LYP functional with SDD basis set optimize the ground state geometries, and carry out time-dependent DFT calculations for the vertical transitions. The results have compared with experiments. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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