臺灣博碩士論文加值系統

本研究以高斯92套裝軟體，6-311G**為基底，限定自洽場方法，分別計算出氯甲烷和氟甲烷系列中，氯原子和氟原子鄰近的電場梯度。我們發現主要是由於誘導效應與負超共軛兩因素，影響氟甲烷系列電場梯度的變化；同時藉由電場梯度的觀點，亦協調了近三十年對負超共軛的爭議；換句話說，我們無法只以上述任一種效應單獨探討氟甲烷系列的衍生物。然而分析氯甲烷系列的電場梯度值，指出負超共軛對其影響極小，甚至可乎略不計。
再者，本研究以原子電荷分析或是天然分布分析，證明早期被物理學家所提出的屏蔽效應。在相似系列的氰基化合物中，我們發現氮-14的核四極偶合常數事實上對於取代基之σ效應幾乎沒有變化，但可以利用包含負超共軛等π效應予以解釋之；這個結論亦被Fenske-Hall分子軌域計算金屬羰基錯合物所支持。所以不管Townes-Dailey曾被質疑其粗糙的假設，我們於此證明最近所提出的利用核磁共振弛緩技術測定氧-17的核四極偶合常數，計算其回饋鍵結電子密度仍是相當可靠。
本研究尚以氯-35和氯-37測定其核四極弛緩速率，是為了證實核磁共振四極核弛緩公式的多用途性；另外測定氘原子的核四極偶合常數，以驗證元始計算方法計算電場梯度的可靠性。影響電場梯度（或核四極偶合常數）的因素，本研究會廣泛且詳細的探討。

The electric field gradients（efg）in the vicinity of fluorine or chlorine atoms in fluoromethanes and chloromethanes have been obtained by spin-restricted Hartree-Fock（RHF）6-311G** calculations using Gaussian 92 package. It is found that both inductive effects and negative hyperconjugation have to be employed to rationalize the trend of efg variations in fluoromethanes. This conclusion indicates that, from the viewpoint of efg, not only does the negative hyperconjugation exist but also supplies reconciliation for the controversy reported in recent three decades. In other words, the stabilization of methane derivatives due to fluorination should not be explained solely by either one of the above-mentioned effects. For the chlorinated analogues, however, analysis the values of efg reveals that negative hyperconjugation is so insignificant as to be negligible.
Furthermore, the so-call shielding effect proposed earlier by physicists is confirmed by natural population analysis or atomic charge analysis. In closely related cyano-contained compounds, therefore, one usually observes that variations of nitrogen-14 nuclear quadrupole coupling constants（NQCC）are virtually invariant toward substituents and can be account for by pi-effects including negative hyperconjugation. This conclusion is supported by Fenske-Hall MO calculations reported for metal carbonyls. Hence, the present study reconfirms the validity of the NMR relaxation method, which uses NQCC（17O）for evaluation of the backbonding electron density a more recently, despite of that the Townes-Dailey assumptions has been questioned in our labs.
Measurements of values quadrupolar relaxation reates and NQCC for 35Cl, 37Cl, 2H have also been conducted in this research in order to verify the versatility of NMR quadrupolar relaxation equation and the reliability of calculated efg by ab initio method, respectively. Factors that would affect the value of efg（or NQCC）have been extensively examined and discussed in detail.

中文摘要．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅰ
英文摘要．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅱ
誌謝．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅲ
目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅳ
表目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅵ
圖目錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅶ
重要的英文縮寫和其中文譯名．．．．．．．．．．．．．．．．．．Ⅷ
第一章、緒論．．．．．．．．．．．．．．．．．．．．．．．．．1
第二章、理論背景．．．．．．．．．．．．．．．．．．．．．．．4
壹、核的簡介與四極核的性質．．．．．．．．．．．．．．．．．．4
貳、電場梯度與核四極偶合常數．．．．．．．．．．．．．．．．．5
參、Townes-Dailey理論．．．．．．．．．．．．．．．．．．．．9
　一、簡介．．．．．．．．．．．．．．．．．．．．．．．．．．9
　二、應用於多鍵系統分子的核四極偶合常數．．．．．．．．．．10
肆、元始計算．．．．．．．．．．．．．．．．．．．．．．．．12
　一、分子軌域模型簡介．．．．．．．．．．．．．．．．．．．12
　二、基底．．．．．．．．．．．．．．．．．．．．．．．．．14
　三、電場梯度值的計算原理．．．．．．．．．．．．．．．．．18
　四、限定自洽場與非限定自洽場計算方法簡介．．．．．．．．．19
　五、分析方法．．．．．．．．．．．．．．．．．．．．．．．20
伍、核磁共振基本原理．．．．．．．．．．．．．．．．．．．．23
　一、核在磁場下所受的影響．．．．．．．．．．．．．．．．．23
　二、核磁共振的原理．．．．．．．．．．．．．．．．．．．．24
　三、核磁共振弛緩．．．．．．．．．．．．．．．．．．．．．24
　四、四極核弛緩．．．．．．．．．．．．．．．．．．．．．．26
陸、測定鍵強的簡單回顧．．．．．．．．．．．．．．．．．．．27
柒、超共軛與負超共軛．．．．．．．．．．．．．．．．．．．．28
　一、超共軛．．．．．．．．．．．．．．．．．．．．．．．．28
　二、負超共軛．．．．．．．．．．．．．．．．．．．．．．．29
第三章、實驗與計算方法．．．．．．．．．．．．．．．．．．．．33
　壹、光譜實驗．．．．．．．．．．．．．．．．．．．．．．．．33
　一、儀器設備．．．．．．．．．．．．．．．．．．．．．．．33
　二、藥品來源．．．．．．．．．．．．．．．．．．．．．．．33
　三、實驗步驟．．．．．．．．．．．．．．．．．．．．．．．33
貳、元始計算．．．．．．．．．．．．．．．．．．．．．．．．35
　一、條件．．．．．．．．．．．．．．．．．．．．．．．．．35
　二、計算流程．．．．．．．．．．．．．．．．．．．．．．．36
第四章、結果與討論．．．．．．．．．．．．．．．．．．．．．．37
壹、不同基底的影響．．．．．．．．．．．．．．．．．．．．．37
貳、相同分子內同位素的弛緩速率．．．．．．．．．．．．．．．37
參、以實驗與計算含氘原子化合物的電場梯度值．．．．．．．．．38
肆、CH4-nCln與CH4-nFn（n＝1、2、3、4）系列鹵素之電場梯度變化38
　一、影響電場梯度變化的主要因素．．．．．．．．．．．．．．40
　二、電場梯度與各成分比例的關係．．．．．．．．．．．．．．41
　三、誘導、負超共軛、立體效應的各項間接證據．．．．．．．．42
　四、氟甲烷系列負超共軛效應的爭論．．．．．．．．．．．．．44
伍、屏蔽效應：氰基或羰基上之碳對氮或氧原子．．．．．．．．．46
　一、氰基有機化合物．．．．．．．．．．．．．．．．．．．．46
　二、過渡金屬羰基錯合物．．．．．．．．．．．．．．．．．．48
陸、氰基化合物氮原子的電子分布及電場梯度變化．．．．．．．．49
　一、CH3-nClnCN（n＝1、2、3）的電子分布與電場梯度．．．．．50
　二、CH2XCN（X＝H、Cl、Br、I）的電子分布與電場梯度．．．．．50
　三、乙烯基（ethylene）氰化物的π系統變化．．．．．．．．．51
第五章、結論與未來展望．．．．．．．．．．．．．．．．．．．．52
表格．．．．．．．．．．．．．．．．．．．．．．．．．．．．53
圖形．．．．．．．．．．．．．．．．．．．．．．．．．．．．63
參考文獻．．．．．．．．．．．．．．．．．．．．．．．．．．72
自述．．．．．．．．．．．．．．．．．．．．．．．．．．．．77

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