臺灣博碩士論文加值系統

In the dissertation, the reaction of C(3p) + SiH4 is investigated by combining electronic structure and statistical calculations. The reaction was found to from an initial a van der Waals complex in the entrance channel, intersystem crossing (ISC) from the triplet to the singlet potential surface. The study provides insight on the molecular level and shed light on the non-adiabatic reaction dynamics of silicon, which is distinct from isovalent carbon systems. On both triplet and singlet surface, we use CCSD/cc-pVTZ to optimize complexes, intermediates, transition states and products. Energies are further calculated by CCSD/CBS with CCSD/cc-pVTZ zero-point energy correction. The statistical RRKM theory is employed in calculating rate constant and evolution of concentration with time. The major product at triplet pathways is predicted to be Si-CH3 and at singlet pathways, HSi-CH2.
The formation of organic amide polymers via carbonyl–amino group linkages in carbon monoxide and ammonia bearing energetically processed ices of astrophysical relevance is investigated with one carboxyl group and an increasing number of amine moieties starting with formamide (45 u), urea (60 u), and hydrazine carboxamide (75 u). The second group consists of species with two carboxyl (58 u) and up to three amine groups (73 u, 88 u, and 103 u). The formation and polymerization of these linkages from simple inorganic molecules via formamide und urea toward amide polymers is discussed in an astrophysical and astrobiological context. Our results show that long chain molecules, which are closely related to polypeptides, easily form by energetically processing simple, inorganic ices at very low temperatures and can be released into the gas phase by sublimation of the ices in star-forming regions. Our experimental results were obtained by employing reflectron time-of-flight mass spectroscopy, coupled with soft, single photon vacuum ultraviolet photoionization; they are complemented by theoretical calculations. We use b3lyp/cc-pVTZ to optimize neutral and ionic 2-oxo-2-triazylacetaldehyde and N-formylhydrazinecarboxamide. Energies are calculated by CCSD/CBS with b3lyp/cc-pVTZ zero-point energy correction. The ionization energies are obtained by taking the energy difference between corresponding neutral and ionic species. The result is compared with experiments.

Table of content
ABSTRACT……………………………………………………………………………………………………………………………ⅰ
TABLE OF CONTENTS……………………………………………………………………………………………………ⅱ

Chapter 1. Pathways of dehydrogenation reaction of C(3P) + SiH4 collision
1. Introduction…………………………………………………………………………………………………1
2. Theoretical methods………………………………………………………………………………2
2.1 RRKM(Rice-Ramsperger-Kassel-Marcus theory)………………3
2.2 Complete basis set(CBS) ………………………………………………………………3
2.3 Concentration evaluation and branching ratio…………4
2.4 CPMCSCF……………………………………………………………………………………………………………4
3. Results and discussion………………………………………………………………………5
3.1 Reaction paths on triplet potential surface……………5
3.1.1 Reaction paths………………………………………………………………………………5
3.1.2 products………………………………………………………………………………………………8
H atom dissociation products………………………………………………8
H2-elimination products……………………………………………………………8
3.1.3 Evolution of concentrations with time…………………8
0 kJ/mol collision energy………………………………………………………9
13 kJ/mol collision energy…………………………………………………10
31 kJ/mol collision energy…………………………………………………11
3.2 Reaction paths on singlet potential surface…………12
3.2.1 Reaction paths……………………………………………………………………………12
3.2.2 Products……………………………………………………………………………………………14
H atom dissociation products……………………………………………15
H2-elimination products ………………………………………………………15
3.2.3 Evolution of concentrations with time………………15
0 kJ/mol collision energy……………………………………………………16
13 kJ/mol collision energy…………………………………………………17
31 kJ/mol collision energy…………………………………………………18
3.3 Compare…………………………………………………………………………………………………………19
3.3.1 Compare with intermediate 1i2 and 3i2………………19
3.3.2 Compare with different collision energy…………20
Triplet potential surface……………………………………………………20
Singlet potential surface……………………………………………………20
3.3.3 Compare with experiment……………………………………………………21
3.3.4 Compare with Si+SiH4……………………………………………………………21
3.3.5 Compare with C2H4……………………………………………………………………22
4. Conclusion……………………………………………………………………………………………………22
Table 1……………………………………………………………………………………………………………………………24
Table 2……………………………………………………………………………………………………………………………27
Table 3……………………………………………………………………………………………………………………………28
Table 4……………………………………………………………………………………………………………………………29
Table 5……………………………………………………………………………………………………………………………29
Table 6……………………………………………………………………………………………………………………………29
Figure 1…………………………………………………………………………………………………………………………30
Figure 2…………………………………………………………………………………………………………………………31
Figure 3…………………………………………………………………………………………………………………………32
Figure 4…………………………………………………………………………………………………………………………33
Figure 5…………………………………………………………………………………………………………………………34
Figure 6…………………………………………………………………………………………………………………………36
Figure 7…………………………………………………………………………………………………………………………38
Figure 8…………………………………………………………………………………………………………………………43
Figure 9…………………………………………………………………………………………………………………………44
Figure 10a……………………………………………………………………………………………………………………45
Figure 10b……………………………………………………………………………………………………………………46
Figure 10c……………………………………………………………………………………………………………………47
Figure 11a……………………………………………………………………………………………………………………48
Figure 11b……………………………………………………………………………………………………………………49
Figure 11c……………………………………………………………………………………………………………………50
Figure 12………………………………………………………………………………………………………………………51
Table S1…………………………………………………………………………………………………………………………60
Table S2…………………………………………………………………………………………………………………………61
Table S3…………………………………………………………………………………………………………………………61
Table S4…………………………………………………………………………………………………………………………62
Table S5…………………………………………………………………………………………………………………………62
Figure S1………………………………………………………………………………………………………………………63
REFERENCE………………………………………………………………………………………………………………………64

Chapter 2. Formation of amide polymers via carbonyl-amino group linkages in energetically processed ices of astrophysical relevance
1. Introduction………………………………………………………………………………………………67
2. Theoretical methods……………………………………………………………………………70
2.1 Complete basis set(CBS) ……………………………………………………………………70
3. Results……………………………………………………………………………………………………………70
3.1 N-formylhydrazinecarboxamide…………………………………………………71
3.2 2-oxo-2-triazylacetaldehyde……………………………………………………73
3.3 Compare with experiment………………………………………………………………74
4. Conclusion……………………………………………………………………………………………………75
Figure 1…………………………………………………………………………………………………………………………76
Table 1……………………………………………………………………………………………………………………………77
REFERENCE………………………………………………………………………………………………………………………79

part A
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