臺灣博碩士論文加值系統

The reaction of ground-state boron atom, B(2Pj), with hydrogen cyanide, HCN(1Σ+), is investigated theoretically to explore possible pathways boron-bearing species. Three collision complexes c1, c2 and c3 are identified. The optimized geometries and harmonic frequencies of the intermediates, transition states, and products are obtained by using the unrestricted B3LYP/cc-pVTZ method, and the corresponding CCSD(T)/cc-pVTZ energies are calculated. The rate constants for the reaction paths are computed according to RRKM theory at collision energies of 0-10 kcal/mol, and the most probable paths are subsequently determined.
The adiabatic ionization potentials of C5N and C5O are investigated with ab initio electronic structure calculations. The optimized geometries and harmonic frequencies of likely isomers for neutral and ionic C5N and C5O species are obtained at the level of the hybrid density functional theory, B3LYP/cc-pVTZ; their CCSD(T)/cc-pVTZ energies with B3LYP/cc-pVTZ zero-point energy corrections are computed for C5N and C5O species. The ionization potentials of each isomer for C5N and C5O species are estimated by taking the energy difference with zero-point energy corrections between the respective ionic and neutral counterparts. The results would be compared with the experimental measurements.
Prediction of the excited-state properties of [Au(4-dmapy)2][AuCl2], [Ag(4-dmapy)2][AgCl2], and [Cu(4-dmapy)2][CuCl2] were carried out theoretically. The electronic structures of the ground state and low-lying excited states are computed by CASSCF and CIS methods. The absorption spectrum of [Cu(4-dmapy)2][CuCl2] is simulated.

TABLE OF CONTENTS
Abstract i
Chapter 1. Pathways of the reaction of B(2Pj) with hydrogen cyanide, HCN(1Σ+) 1
1. Introduction 1
2. Theoretical Methods 2
2.1 Ab initio electronic structure calculation for the reaction path predictions 2
2.2 RRKM rate constant calculations 3
2.3 Variational RRKM rate constant calculations 3
3. Results and Discussions 4
3.1 Collision complexes 4
3.1.1 c1 5
3.1.2 c2 5
3.1.3 c3 6
3.2 Reaction pathways 6
3.2.1 H dissociation products 6
3.2.2 Reaction paths of c1 6
3.2.3 Reaction paths of c2 7
3.2.4 Reaction paths of c3 7
3.2.5 The most probable paths of c1, c2, c3 7
3.2.6 The most probable paths of complexes 8
4. Conclusions 8
Reference 9
Table I 12
Table II 15
Figure 1 17
Figure 2 18
Figure 3 19
Figure 4 20
Figure 5 21
Figure 6 22
Figure 7 25
Figure 8 26
Figure 9 27
Chapter 2. Calculations for the ionization potentials of C5N and C5O 29
1. Introduction 29
2. Results and Discussions 30
2.1 Properties of calculated structures 31
2.1.1 C5N 31
2.1.2 1C5N+ 31
2.1.3 3C5N+ 31
2.1.4 C[C3]CN 32
2.1.5 1C[C3]CN+ 32
2.1.6 3C[C3]CN+ 32
2.1.7 [C2N]C3 33
2.1.8 1[C2N]C3+ 33
2.1.9 3[C2N]C3+ 33
2.1.10 [C4]CN 34
2.1.11 1[C4]CN+ 34
2.1.12 3[C4]CN+ 34
2.1.13 [C5N] 35
2.1.14 1[C5N]+ 35
2.1.15 3[C5N]+ 35
2.1.16 1C5O 36
2.1.17 3C5O 36
2.1.18 C5O+ 36
2.1.19 1C[C3]CO 37
2.1.20 3C[C3]CO 37
2.1.21 C[C3]CO+ 37
2.1.22 1[C2O]C3 38
2.1.23 3[C2O]C3 38
2.1.24 [C2O]C3+ 38
2.1.25 1[C4]CO 39
2.1.26 3[C4]CO 39
2.1.27 [C4]CO+ 39
2.1.28 1[C5O] 40
2.1.29 3[C5O] 40
2.1.30 [C5O]+ 40
2.2 Vibrational frequencies and rotational constants 41
2.3 Ionization potential energies 41
3. Conclusions 42
Reference 43
Table I 47
Table II 49
Table III 51
Table IV 52
Figure 1 53
Figure 2 55
Figure 3 57
Figure 4 58
Figure 5 59
Figure 6 60
Chapter 3. Prediction the excited-state properties of dinuclear coinage metal (I) complexes: [M(4-dmapy)2][MCl2] (4-dmapy = 4-dimethylaminopyridine, M = Au, Ag, Cu) 61
1. Introduction 61
2. Results and Discussions 61
2.1 The ground states of [M(4-dmapy)2][MCl2] 62
2.1.1 [Au(4-dmapy)2][AuCl2] 62
2.1.2 [Ag(4-dmapy)2][AgCl2] 62
2.1.3 [Cu(4-dmapy)2][CuCl2] 63
2.2 The excited states of [M(4-dmapy)2][MCl2] 63
2.2.1 The third excited state of [Ag(4-dmapy)2][AgCl2] 63
2.2.2 The second excited state of [Cu(4-dmapy)2][CuCl2] 63
2.3 Simulated absorption spectra of [Cu(4-dmapy)2][CuCl2] 64
3. Conclusions 64
Reference 65
Figure 1 67
Figure 2 68
Figure 3 69
Figure 4 70
Figure 5 71
Figure 6 72
Figure 7 73

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