臺灣博碩士論文加值系統

本實驗室以前曾研究過許多結構相似分子之光物理現象與其氫鍵結合物之放射光譜，論文之第一部份討論，儘管其基態結構相似，但激發態之性質卻相差很大，所以我們用理論計算算出此分子之HOMO、LUMO看電子雲在激發態時移動之方向，並且計算接合物之新生振動頻率，再將此數據與吸收光譜、放光光譜做一比較與討論。
第二部份是先導證由吸光光譜與放射光譜求取接合物之結合常數之公式，然後由光譜中選取適當之波長，作此運算。結果顯示由放射光譜可得之結合常數比較合理，我們並用量子理論求取△G值，並進一步求取得結合常數（Ka），進一步改變溶劑之介電常數（dielectric constant）求取相對之結合常數並與實驗數據值比較。

In our laboratory, we have done a lot of study on the emission of hydrogen-bonded complex in the past few years. We want to find some regulations for the fluorescence study.
On the first part of my research, we study the fluorescence of these chemical compounds. Although the chemical structure is similar, the excited phenomena of these compounds is very different, in the meantime, we use the molecular calculation (HyperChem) to estimated the shift direction of electron cloud in LUMO state of these compounds. The results show the hydrogen-bonded exciplex formation is observed for compound PVN. More over, we calculated the vibration frequency of the hydrogen-bonded complex, compound PVN and triethylamine which may relate to the intensity of exciplex.
For the second portion of research, we derive the association const for formation of hydrogen bonded complex from the related absorption spectra and emission spectra. In our results, shows that the association constant estimated from emission spectra in various solvent has the most reasonable value according to the variation direction of dielectric constants of the solvents. In the mean while, we use the molecular calculation (Gaussian) to estimated the Gibbs free energy of formation of hydrogen-bonded complex, then convert it to the association constants. At final we verify the dielectric constants to see the variation of association constants.
The association constants from experiment measurement and theory calculation were presented and discussed.

文獻回顧………………………………………………………………………1
1. Exciplex之形成……………………………………………………….1
2.由氫鍵形成的激發錯合體………………………………………………5
3.溶劑效應…………………………………………………………………9
4.理論計算的介紹…………………………………………………………13
5.公式之推導………………………………………………………………21
Part 1：分子接合物形成前後，鍵長、鍵角、酸鹼度與振動頻率之改變26
計算方法………………………………………………………………………27
計算的化合物…………………………………………………………………28
實驗的結果與討論……………………………………………………………30
結論……………………………………………………………………………33
Part 2：由吸收光譜、放射光譜和理論計算來比較結合常數……………34
藥品…………………………………………………………………………35
儀器…………………………………………………………………………36
計算方法…..………………………………………………………………37
實驗的結果與討論…………………………………………………………38
結論…………………………………………………………………………50
參考文獻………………………………………………………………………52

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