本論文以實驗室自行架設的超快時間解析螢光光譜儀與超快瞬態吸收光譜儀研究4-硝基聯苯(4-nitobiphenyl, 4-NBP)於acetonitrile (ACN)、methanol (MeOH)、triacetin (Tri)與cyclohexane (CHX)四種溶劑中的激發態緩解動力學，並在理論計算的幫助下解讀4-NBP的激發態緩解機制。在本論文的實驗中我們皆以310 nm的飛秒脈衝雷射將4-NBP激發至S2(π, π*)態。實驗與計算結果顯示4-NBP的激發態緩解機制在所有溶劑中都類似，4-NBP在被激發至S2(π, π*)態後主要經由internal conversion (IC)緩解至S1(n, π*)態，此IC時間常數為< 100 fs，當中少部分的S2(π, π*)態與符合El-Sayed rule的triplet state進行intersystem crossing (ISC)。 S1(n, π*)態隨後再與符合El-Sayed rule的triplet state進行ISC，此ISC時間常數之數量級約為1 ps。而4-NBP在triplet manifold中的緩解機制則隨溶劑而有所不同，在ACN與CHX中，從ISC接收態緩解至最低能量的triplet state T1的過程只需要一個時間常數來描述，而在MeOH與Tri中，此過程因多了solvent specific interaction的影響而變得較複雜，需要兩個時間常數來描述。最後，從T1回到ground state S0的過程，即T1之lifetime，隨著溶劑極性的減少而有變短的趨勢，從ACN中的 > 50 ns減少到CHX中的約2 ns。與實驗室前人研究的trans-4-nitrostilbene (t-NSB)相比，4-NBP的ISC速率幾乎不受溶劑極性影響，我們認為此現象是因為相較於t-NSB進行主要ISC的起始態為能量受溶劑極性影響較大的S1(π, π*)態，4-NBP進行主要ISC的起始態為能量不太受溶劑極性影響的S1(n, π*)態的緣故。

We investigate the excited-state relaxation dynamics of 4-nitrobiphenyl (4-NBP) in acetonitrile (ACN), methanol (MeOH), triacetin (Tri), and cyclohexane (CHX) solutions using a home-built ultrafast time-resolved fluorescence spectrometer and ultrafast transient absorption spectrometer. With the assistance of theoretical calculations, we propose the excited-state relaxation mechanism of 4-NBP. In all experiments described in this thesis, 4-NBP was excited to the S2(π, π*) state with femtosecond laser pulse at 310 nm. Experimental and computational results indicate a similar excited-state relaxation mechanism for 4-NBP in all solvents. Upon excitation to the S2(π, π*) state, it predominantly undergoes internal conversion (IC) to the S1(n, π*) state with an IC time constant of < 100 fs. A minor portion of the S2(π, π*) population directly undergoes intersystem crossing (ISC) to a receiver triplet state that is allowed by the El-Sayed rule. Subsequently, the S1(n, π*) state undergoes intersystem crossing (ISC) to an El-Sayed rule allowed receiver triplet state with an ISC time constant of approximately 1 ps. The triplet manifold relaxation mechanism of 4-NBP varies with solvents: in ACN and CHX, the relaxation from ISC receiver triplet state to the lowest-energy triplet state T1 is described by a single time constant, whereas in MeOH and Tri, it becomes more complex due to the influence of solvent-specific interactions, requiring two time constants for description of the relaxation. Finally, the return process from T1 to the ground state S0, i.e., the lifetime of T1, appears to shorten as solvent polarity decreases, from > 50 ns in ACN to approximately 2 ns in CHX. Comparing with trans-4-nitrostilbene (t-NSB) studied previously in our laboratory, the ISC rate of 4-NBP is found to be unaffected by solvent polarity. We attribute this phenomenon to the fact that, compared to t-NSB, the initial state for primary ISC in 4-NBP is the S1(n, π*) state, whose energy is barely affected by solvent polarity.

摘要 i
Abstract ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 NPAHs激發態動力學文獻回顧 2
1.3 本論文研究目的 8
第二章 實驗系統與技術 9
2.1 超快飛秒雷射系統 9
2.1.1 飛秒雷射產生源 10
2.1.2 能量再生放大器 14
2.2 波長調變器: TOPAS 18
2.3 超快瞬態吸收光譜 21
2.3.1 瞬態吸收光譜原理 21
2.3.2 超快瞬態吸收光譜系統架設 23
2.3.3 超快瞬態吸收光譜自動化數據擷取系統 26
2.3.4 儀器響應函數 27
2.3.5 超快瞬態吸收光譜時間延遲校正 29
2.3.6 超快瞬態吸收光譜背景訊號扣除 31
2.4 超快時間解析螢光光譜 34
2.4.1 克爾光閘原理 34
2.4.2 超快時間解析螢光光譜系統架設 36
2.4.3 超快時間解析螢光光譜自動化數據擷取系統 43
2.4.4 儀器響應函數 45
2.4.5 超快時間解析螢光光譜靈敏度與時間延遲校正 47
2.5 實驗藥品配置 55
第三章 實驗結果與討論 56
3.1 靜態吸收光譜 56
3.2 靜態放光光譜 57
3.3 超快時間解析螢光光譜 58
3.4 超快瞬態吸收光譜 66
3.5 DFT理論計算 84
3.6 綜合討論 94
第四章 結論 103
參考文獻 106

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