臺灣博碩士論文加值系統

本論文利用ab initio計算方法，分別研究formyl cyanide以及acetyl cyanide最低的三個singlet excited states，S1、S2和S3，以及最低triplet excited state，T1之平衡結構、電子組態，及電子垂直躍遷的能量。此外，我們也計算了acetyl cyanide在T1位能面沿著C-CN鍵及C-CH3鍵解離反應座標之過渡態結構，並得到在T1位能面進行C-CN鍵及C-CH3鍵解離反應的能障。MP2/6-311+G* level(B3LYP/6-311+G*)計算結果分別為193.7 (170.9) kJ/mole及68.4(83.6) kJ/mole。配合我們實驗結果，以及之前的文獻報告，我們建立一反動態學模型，用以解釋其光分解反應的過程：193 nm光激發分子至S3能態，大部分的分子經由internal conversion (IC)至S2能態後，直接進行C-CN鍵的解離反應，少數的分子由S2經IC及intersystem crossing(ISC)的過程到達T1能態，在T1能態進行C-CN鍵以及C-CH3鍵的解離反應。在S2能態上，adiabatic解離C-CN鍵是很有效率的，我們推測約為2.5 ps，是造成acetyl cyanide傾向解離C-CN鍵的主要原因。最後，我們也討論nonadiabatic recrossing效應對於其反應速率的影響。

目錄
摘要………………………………………………………………………i
目錄………………………………………………………………….…..ii
圖目錄…………………………………………………………………..iv
表目錄……………………………………………………………...…....v 第一章 序論…………………………………………………..………...1
1-1 Norrish TypeⅠ反應…………………………………..……....2
1-2 Carbonyl compounds的光分解反應…………………..….…4
1-3 Acetyl cyanide光分解反應研究之回顧………………..….…7
1-4 本論文的研究………………………………………………….9
1-5 參考文獻………………………………………………………10
第二章 Ab initio及RRKM計算方法與原理………………………...13
2-1 Ab initio計算方法與原理………..………………………….13
2-1-1薛汀格方程式…………………………………………...13
2-1-2 Hartree-Fock方法………………………………………16
2-1-3 Moller-Plesset Perturbation方法……………………….20
2-1-4 Density Function方法…………………………………..22
2-1-5 Configuration Interaction方法………………………….24
2-2 RRKM計算方法與原理………………….…………………25
2-2-1 Microconanical Transition State Theory………………..25
2-2-2 RRKM Theory………………………………………….29
2-3 參考文獻……………………………………………………....30
第三章 Ab initio 計算結果與討論…………………………………..32
3-1 HC(O)CN研究之回顧……………….……..………………..32
3-1-1 HC(O)CN基態之研究…………………………………33
3-1-2 HC(O)CN激發態之研究………………………………35
3-2 CH3C(O)CN研究之回顧…………………………………….40
3-2-1 CH3C(O)CN基態之研究………………………………41
3-2-2 CH3C(O)CN激發態之研究……………………………42
3-3 參考文獻………………………………………………………48
第四章CH3C(O)CN光解反應研究……………………………..……75
4-1 CH3C(O)CN光解反應之回顧…………………………..……75
4-2 CH3C(O)CN飛秒時析光譜研究之結果………………..……78
4-3 CH3C(O)CN的光分解反應機制………….…….……………79
4-4 Adiabatic dissociation on T1 surfaceRRKM calculations
for D3 and D4…………………………………….……...……83
4-5 Effect of nonadiabatic recrossing……………………………84
4-6 參考文獻………………………………………...…………….88
第五章 結語…………………………………………………………..100
圖目錄
圖4-1 短時間尺度瞬時光譜………………………...………….…....91
圖4-2 中等時間尺度瞬時光譜…………………………..…………..92
圖4-3 長時間尺度瞬時光譜………………………………..………..93
圖4-4 具有平面對稱性下，產物態與各能態的correlation關係圖..94
圖4-5 rC-CN與rC-CH3反應座標上，具有平面對稱性下的位能曲線
係及反應途徑示意圖………………….…...…..……………..95
圖4-6 H+HS―→H+HS反應位能圖及激發態HOMO之MO圖…96
圖4-7 A-BC―→A + BC沿著反應座標之位能面示意圖………….97
圖4-8 BrCH2COCl解離反應位能面示意圖…………………………98
圖4-9 Acetyl cyanide在T1位能面光分解反應示意圖……………..99
表目錄
Table 3-1-1(a) Geometrical Parameters of the Ground State of Formyl
cyanide(HF level)……………….…………………..50
Table 3-1-1(b) Vibrational Frequencies of the Ground State of Formyl
cyanide(HF level).……………….……………….…50
Table 3-1-2(a) Geometrical Parameters of the Ground State of Formyl
cyanide(MP2(FU) level).……………….…………...51
Table 3-1-2(b) Vibrational Frequencies of the Ground State of Formyl
cyanide(MP2(FU) level).………………….………...51
Table 3-1-3(a) Calculated Vertical Transition Energy for Formyl
cyanide………………….…………………………...52
Table 3-1-3(b) Calculated Vertical Transition Energy for Acetyl
cyanide……….………………………….…………..52
Table 3-1-4(a) Geometrical Parameters of the S1 State of Formyl
cyanide(CIS level).……….…………………………53
Table 3-1-4(b) Vibrational Frequencies of the S1 State of Formyl
cyanide(CIS level).……….…………………………53
Table 3-1-5(a) Geometrical Parameters of the S2 State of Formyl
cyanide(CIS level)…………….…………………….54
Table 3-1-5(b) Vibrational Frequencies of the S2 State of Formyl
cyanide(CIS level)……………….……….…………54
Table 3-1-6(a) Geometrical Parameters of the S3 State of Formyl
cyanide(CIS level).……………………………….…55
Table 3-1-6(b) Vibrational Frequencies of the S3 State of Formyl
cyanide(CIS level).…………………………….……55
Table 3-1-7(a) Geometrical Parameters of the T1 State of Formyl
cyanide(UHF level).………………….……………..56
Table 3-1-7(b) Vibrational Frequencies of the T1 State of Formyl
cyanide(UHF level).…………………………….…..56
Table 3-1-8(a) Geometrical Parameters of the T1 State of Formyl
cyanide(MP2(FU) level).…………………………...57
Table 3-1-8(b) Vibrational Frequencies of the T1 State of Formyl
cyanide(MP2(FU) level).…………………….……..57
Table 3-1-9(a) Geometrical Parameters of the T1 State of Formyl
cyanide(CIS level).…………………………………58
Table 3-1-9(b) Vibrational Frequencies of the T1 State of Formyl
cyanide(CIS level)…………………….……………58
Table 3-2-1(a) Geometrical Parameters of the Ground State of Acetyl
cyanide(HF/6-311+G*)…………………………….59
Table 3-2-1(b) Vibrational Frequencies of the Ground State of Acetyl
cyanide(HF/6-311+G*)…………………………….61
Table 3-2-2(a) Geometrical Parameters of the Ground State of Acetyl
cyanide(MP2(FU)/6-311+G*)…………….……......60
Table 3-2-2(b) Vibrational Frequencies of the Ground State of Acetyl
cyanide(MP2(FU)/6-311+G*)…………………..….60
Table 3-2-4(a) Geometrical Parameters of the S1 State of Acetyl
cyanide(CIS/6-311+G*)……………….……….…..62
Table 3-2-4(b) Vibrational Frequencies of the S1 State of Acetyl
cyanide(CIS/6-311+G*)………………………..…..65
Table 3-2-5(a) Geometrical Parameters and Frequencies of the S2 State
of Acetyl cyanide(CIS/6-311+G*)………………....63
Table 3-2-5(b) Vibrational Frequencies of the S2 and S3 State of Acetyl
cyanide(CIS/6-311+G*)……………………………65
Table 3-2-6(a) Geometrical Parameters of the S3 State of Acetyl
cyanide (CIS/6-311+G*)…………………………...64
Table 3-2-7(a) Geometrical Parameters of the T1 State of Acetyl
cyanide(UHF/6-311+G*)…………….………….…66
Table 3-2-7(b) Vibrational Frequencies of the T1 State of Acetyl
cyanide(UHF/6-311+G*)……….………………….68
Table 3-2-8(a) Geometrical Parameters of the T1 State of Acetyl
cyanide(UMP2(FU)/6-311+G*)…………………....67
Table 3-2-8(b) Vibrational Frequencies of the T1 State of Acetyl
cyanide(UMP2(FU)/6-311+G*)……………….…...68
Table 3-2-9(a) Geometrical Parameters of the T1 State of Acetyl
cyanide(CIS/6-311+G*)…………………………....69
Table 3-2-9(b) Vibrational Frequencies of the T1 State of Acetyl
cyanide(CIS/6-311+G*)…………………………....70
Table 3-2-10(a) Geometrical Parameters of the TS of Acetyl cyanide
on T1 State(UMP2(FU)/6-311+G*)….….………...71
Table 3-2-10(b) Vibrational Frequencies of the TS of Acetyl cyanide
on T1 State(UMP2(FU)/6-311+G*)………..……...72
Table 3-2-11(a) Geometrical Parameters of the TS of Acetyl cyanide on
T1 State(UB3LYP/6-311+G*)………..………..….73
Table 3-2-11(b) Vibrational Frequencies of the TS of Acetyl cyanide on
T1 State(UB3LYP/6-311+G*)………...………..…74

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