我們透過飛秒激發-探測光譜技術結合飛行時間質譜(TOF-MS)技術，量測MNMA (methyl[(1,2,3,4-tetrahydronaphthalen-2-yl)methyl]amine)及MPBA (N-methyl-4-phenylbutylamine)分子於光游離-光裂解機制下所產生的離子損耗瞬時訊號，以研究電子供體受體陽離子的緩解動力學過程。我們以波長為266 nm激發雷射脈衝透過1+1 REMPI的方式激發分子使苯環端局部游離，以形成正電荷主要位於苯環端的初始陽離子D1/D2 state，隨後陽離子會透過內轉換過程從D1/D2 state緩解至正電荷於胺基端的D0 state，此過程相當於電荷轉移(charge transfer)。在緩解的過程中，我們再利用另一道低脈衝能量的探測雷射脈衝將陽離子激發至更高的能態造成母陽離子裂解成碎片離子，進而獲得母陽離子的離子損耗瞬時訊號，並以此瞬時訊號研究MNMA及MPBA陽離子的緩解動力學過程。我們結合理論計算及預期無電荷轉移之PPAL (phenylpropyl alcohol)陽離子的實驗結果，確定由離子損耗瞬時訊號擬合結果之τ1為陽離子D1/D2 state緩解至陽離子D0 state的電荷轉移時間常數(0.07~0.28 ps)，陽離子D0 state的初始構型應與中性S0 state主要構型雷同，但由於正電荷從苯環端轉移至胺基端，導致胺基端受庫倫作用力驅動而大幅度向苯環端靠近，在時間常數τ2 (7~26 ps)後緩解至較穩定構型。最後，較穩定構型會繼續發生平衡緩解至以最穩定構型為主的D0 state構型，此過程可能需克服較大的能障，使得其時間常數τ3 較長(210~550 ps)。

In this thesis, we measured the ion depletion transient of MNMA (methyl[(1,2,3,4-tetrahydronaphthalen-2-yl)methyl]amine) and MPBA (N-methyl-4-phenylbutylamine) molecules through the photoionization-photofragmentation mechanisms to investigate the relaxation dynamics of electron donor-acceptor molecular cations by using femtosecond pump-probe spectroscopy combined with time-of-flight mass spectrometry (TOF-MS).We used a pump pulse at 266 nm to excite the molecules through 1+1 resonance-enhanced multiphoton ionization (1+1 REMPI), leading to local ionization at the phenyl ring and forming initial cations with the positive charge predominantly located at the phenyl ring site in the D1/D2 state. The cations subsequently relaxed to the D0 state, in which the positive charge is located at the amine site, via internal conversion that correspond to a charge transfer process. During the relaxation process, another probe laser pulse with a low pulse energy was used to excite the cations to higher energy states, causing the parent cations to fragment. This provided parent ion depletion transients, which reveal the relaxation dynamics of MNMA and MPBA cations. We combined theoretical calculations and experimental results for PPAL (phenylpropyl alcohol) cations, which are expected to exhibit no charge transfer to confirm that τ1 obtained from kinetics fitting of the ion depletion transients is due to the charge transfer for the relaxation from the D1/D2 state to the D0 state (0.07~0.28 ps). Additionally, the initial conformation of the cation in the D0 state is expected to be similar to the major conformation of the neutral S0 state. Subsequently, as the positive charge transfers from the phenyl ring site to the amine site, the amine group is driven by Coulombic forces to move significantly closer to the phenyl ring group, relaxing to a more stable conformation with the time constant τ2 (7~26 ps). Finally, this more stable conformation continues to undergo an equilibrium relaxation to the D0 state distribution dominated by the most stable conformation. This process probably requires overcoming a larger energy barrier, leading to the observed longer time constant τ3 (210~550 ps).

目錄
摘要 i
Abstract ii
誌謝 iii
目錄 v
第一章 緒論 1
1.1 引文 1
1.2 文獻回顧 3
1.3 研究動機 10
第二章 實驗方法與技術 15
2.1 飛秒激發-探測技術 15
2.2 共振增強多光子游離技術 17
2.3 激發-探測光激發-光游離以及激發-探測光游離-光裂解 18
2.3.1 激發-探測光激發-光游離機制 (Pump-Probe PE-PI) 18
2.3.2 激發-探測光游離-光裂解機制 (Pump-Probe PI-PF) 18
2.4 飛秒脈衝雷射系統 20
2.4.1 振盪器系統 21
2.4.2 脈衝能量放大器 28
2.5 波長調變裝置 35
2.5.1 三倍頻非線性光學混頻區-Third Harmonic Generator 36
2.5.2 波長調變器：TOPAS 37
2.5.3 和頻非線性光學混頻區-Sum Frequency Generator 40
2.5.4 二倍頻非線性光學區-Second Harmonic Generator 42
2.6 分子束系統 43
2.6.1 超音速分子束 44
2.6.2 分子束樣品進樣裝置 48
2.6.3 分子束系統架設 48
2.7 飛行時間質譜儀 51
2.8 實驗光路設計 54
2.9 訊號擷取系統 57
2.10 儀器響應函數 61
2.11 藥品來源 62
第三章 實驗結果 63
3.1 MNMA及MPBA分子之1+1 REMPI質譜圖分析 63
3.2 母離子與碎片離子訊號對激發雷射脈衝能量的相依性 65
3.2.1 MNMA分子質譜訊號對激發雷射脈衝能量相依性 65
3.2.2 MPBA分子質譜訊號對激發雷射脈衝相依性 68
3.3 MNMA激發-探測光游離-光裂解實驗條件 70
3.3.1 激發及探測脈衝能量比例對離子瞬時訊號之影響 70
3.3.2 陽離子損耗瞬時訊號驗證 73
3.3.3 離子損耗瞬時訊號對探測雷射脈衝能量之相依性 75
3.3.4 離子損耗率之量測 77
3.3.5 離子損耗率對雷射脈衝能量的相依性 79
3.3.6 各探測波長下測量離子損耗率所使用之探測雷射脈衝能量條件 83
3.4 MNMA離子損耗瞬時訊號及超快時間解析離子光分解光譜 85
3.4.1 短時間及極短時間尺度之MNMA陽離子損耗瞬時訊號 85
3.4.2 中時間與長時間尺度之MNMA陽離子損耗瞬時訊號 88
3.4.3 MNMA陽離子損耗瞬時訊號之動力學模型擬合結果 92
3.4.4 MNMA陽離子超快時間解析光分解光譜 99
3.5 MPBA離子損耗瞬時訊號及超快時間解析離子光分解光譜 105
3.5.1 MPBA陽離子損耗瞬時訊號 105
3.5.2 MPBA陽離子損耗瞬時訊號之動力學模型擬合結果 108
3.5.3 MPBA陽離子超快時間解析光分解光譜 112
3.6 無電荷轉移對照組 114
3.6.1 PPAL分子質譜圖 115
3.6.2 PPAL陽離子損耗瞬時訊號 115
3.6.3 PPAL陽離子損耗瞬時訊號之動力學模型擬合結果 119
3.6.4 PPAL超快時間解析離子光分解光譜 124
第四章 理論計算與綜合討論 125
4.1 MNMA分子之理論計算與實驗結果討論 125
4.2 MPBA分子之理論計算與實驗結果討論 138
第五章 結論 150
參考文獻 152
附錄 156
附錄 Ⅰ MNMA陽離子損耗瞬時訊號之動力學模型擬合結果 156
附錄 Ⅱ MNMA分子中性S0 state分子構型計算結果 172
附錄 Ⅲ MPBA分子中性S0 state分子構型計算結果 175
附錄 Ⅳ MNMA及MPBA陽離子D0 state構型計算結果 179
附錄 Ⅴ MNMA中性S0 state 36種構型實際結構圖 180
附錄 Ⅵ MPBA中性S0 state 17種構型實際結構圖 182
附錄 Ⅶ MNMA陽離子D0 state 23種構型實際結構圖 183
附錄 Ⅷ MPBA陽離子D0 state 13種構型實際結構圖 185

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