Acetyl cyanide分子的光分解反應研究｜國立清華大學博碩士論文庫

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研究生：	鍾宇傑 Chung Yu-Chieh
論文名稱：	Acetyl cyanide分子的光分解反應研究
指導教授：	鄭博元 Cheng Po-Yuan
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2000
畢業學年度：	88
語文別：	中文
論文頁數：	102
中文關鍵詞：	光分解反應、雷射、過渡態
外文關鍵詞：	photodissociation reaction, Laser, transition state, acetyl cyanide
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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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