臺灣博碩士論文加值系統

本論文研究分為三部分，在第一章中，我們以MP2 及 CCSD(T) 的理論計算方法，配合 aug-cc-pVDZ 和 aug-cc-pVTZ 等基底函數來研究 XNBNgF ( X = CH3, HO, NC, HCC, OB, H2N ; Ng = Ar, Kr )這類型惰性氣體分子的幾何結構、相對能量及可能發生的分解途徑。在較高階理論方法下，我們發現XNBArF分子的B-Ar及Ar-F鍵長分別為1.78Å及2.02Å左右;在XNBKrF分子的B-Kr及Kr-F鍵長分別為1.93Å及2.03Å左右。而在XNBNgF分子穩定性方面，我們主要探討( 1 ) XNBNgF → XNB + Ng + F及( 2 ) XNBNgF → XNBF +Ng兩種的分解反應，反應( 1 )當Ng = Ar時，反應能約為2 ~ 10 kcal/mol;當Ng = Kr時，反應能約為20 ~ 25 kcal/mol。反應( 2 )當Ng = Ar時，反應能約為 -145 ~ 155 kca/mol，能障約為12 ~ 17 kcal/mol;當Ng = Kr時，反應能約為 -120 ~ 130 kcal/mol，能障約為22 ~ 25 kcal/mol;最後，由電荷分佈圖中，我們發現Ng-B為共價鍵的特性，而F-Ng為離子鍵的特性。最後，結果顯示XNBNgF這類型分子有可能穩定的存在。

在第二章中我們用MP2 以及 CCSD(T) 的理論計算方法，配合 aug-cc-pVDZ 和 aug-cc-pVTZ 等基底函數來計算XNgY這類型惰性氣體分子 ( HBeNgF, FBeNgF, OBNgF, HNBNgF, NCNgH, HCCNgF, CNNgH, OBONgH, FNgH ) 的幾何結構相對能量以及可能發生的分解途徑。研究結果顯示，鈍氣原子 ( Ng = He, Ar, Kr ) 除了能與 H 及 F 鍵結外，也可與 B、C、N、O 等原子形成具有不同程度穩定性的化學鍵。且大部分分子在當Ng = He時都相當不穩定，而在Ng = Ar, Kr時，除了少數鈍氣分子如FBeArF及HBeArF，因其bending分解路徑之能量障礙太低，只有約5 kcal/mol。而其餘的分子在兩種反應路徑下皆有約10 kcal/mol以上的反應能量障礙，因此有可能在低溫環境下被實驗所偵測出來。

在第三章中，我們以Ab initio中MP2的理論方法配合6-31+G**及Dunning’s Correlation Consistent Basis Sets ( aug-cc-pVnZ, n = D,T )，來研究多種含兩個以上鈍氣原子的分子( FArBeArF、FArBNNBArF、FArBNCCNBArF、FArBNBeNBArF、FB(NBArF)2、B(NBArF)3、Trans-FArBNHC=CHNBArF、HC(NBArF)3、O(HBArF)2、F3NgB3O3 、F3Ng2B3O3和F3Ng3B3O3 )之最佳幾何結構及相對能量的計算。在分子穩定性方面，我們主要探討這類型化合物當分解出一個Ng原子時有可能發生的線性和Bending單分解反應途徑;並藉由觀察反應途徑中分子所進行的相對能量大小，初步估計化合物之穩定性。在較大的基底函數下，我們發現含多個惰性氣體的分子在線性分解方面都有吸熱10 ~ 20 kcal/mol左右;在Bending分解方面都約放熱 -150 ~ 160 kcal/mol以上，但少數F3ArB3O3 、F3Ar2B3O3和F3Ar3B3O3分子，在Bending分解時，由於反應能障太低，只有5 ~ 7 kcal/mol而導致分子不穩定。其餘的分子就兩反應路徑相對能量來看都有可能穩定存在。

This thesis consists of three chapters. In chapter one, the structures, relative energies and energy barriers of possible dissociation pathways of the new noble-gas molecules XNBNgF ( Ng = Ar, Kr ) have been calculated by MP2 and CCSD(T) methods. For XNBArF the highest-level calculation shows that the reaction energies of the two dissociation pathways ( 1 ) XNBArF → XNB + Ar + F and ( 2 ) XNBArF → XNBF + Ar are 2 ~ 10 and -145 ~ 155 kcal/mol respectively, and the barriers of the pathway ( 2 ) is 12 ~ 17 kcal/mol. For XNBKrF the reaction energies are 20 ~ 25 and -120 ~ 130 kcal/mol respectively, and the barriers of the pathway ( 2 ) is 22 ~ 25 kcal/mol. The population analysis indicates the covalent character of the B-Ng bonds and the ionic character of the Ng-F bonds. A portion of the calculated results shows the XNBNgF ( Ng = Ar, Kr ) could be dymamically stable.

In chapter two of this thesis, high-level correlated electronic structure calculation has been performed on the new noble-gas molecules XNgY ( HBeNgF, FBeNgF, OBNgF, HNBNgF, NCNgH, HCCNgF, CNNgH, OBONgH, FNgH; Ng = He, Ar, Kr ). In the current study, we found the noble-gas atoms not only can bond with H and F atoms, but they can also bond with B、C、N、O atoms. The result shows that all almost XHeY molecules were not stable exist. Except for FNgBeF and FNgBeH ( Ng = Ar, Kr ) which the bending barriers were so lower ( about 5 kcal/mol ) were not stable exist. The other XNgY ( Ng = Ar, Kr ) molecules were found to have higher energy barriers ( about over 10 kcal/mol ) for both unimolecular dissociation pathways. Thus, theses XNgY ( Ng = Ar, Kr ) could be dynamically stable species.

In chapter three, high-level ab initio molecular orbital theory is used to calculate the geometries, vibrational frequencies, and relative energies of the new molecules which contain more than one noble-gas atoms. ( such as FArBeArF, FArBNNBArF, FArBNCCNBArF, FArBNBeNBArF, FB(NBArF)2, B(NBArF)3, Trans-FArBNHC=CHNBArF, HC(NBArF)3, O(HBArF)2, F3NgB3O3, F3Ng2B3O3 and F3Ng3B3O3 ) For the stable character of noble-gas molecules, the relative energies of the two unimolecular dissociation pathways, linear and bending dissociation pathways were calculated. The higher-level calculation shows that the reaction energies of the two unimolecualr dissociation pathways are 10 ~ 20 and -150 ~ 160 kcal/mol respectively. So we speculate these molecules should be stable exist, except for the portion of molecules ( such as F3ArB3O3, F3Ar2B3O3 and F3Ar3B3O3 ) which their barriers of bending reactant were so lower ( about 5 ~ 7 kcal/mol ) that they could not form stable compounds . Thus we suggest these molecules maybe could be found at experiment in the future.

總目錄
頁次
中文摘要………………………………………………………………..iii
英文摘要………………………………………………………………...vi
第一章 新型鈍氣原子之分子XNBNgF ( X = CH3, OB, HO, NC, HCC, H2N; Ng = Ar, Kr )的理論預測

1.1 前言…………………………………………………………..1-2
1.2 計算方法……………………………………………………..1-4
1.3 結果與討論…………………………………………………1-15
1.4 結論………………………………………………………....1-20
感謝………………………………………………………...........1-21
參考文獻…………………………….……………………..........1-22
圖表……………………………………………………………...1-25

第二章 鈍氣原子與第二週期元素的鍵結之研究
2.1 前言…………………………………………………………..2-2
2.2 計算方法……………………………………………………..2-3
2.3 結果與討論…………………………………………………..2-4
2.4 結論…………………………………………………………2-10
感謝……………………………………………………………...2-11
參考文獻………………………………………………………...2-12
圖表……………………………………………………………...2-15
第三章 含多個鈍氣原子之分子的穩定性探討
3.1 前言…………………………………………………………3-2
3.2 計算方法……………………………………………………3-3
3.3 結果與討論…………………………………………………3-4
3.4 結論…………………………………………………………3-7
感謝……………………………………………………………...3-8
參考文獻………………………………………………………...3-9
圖表……………………………………………………………...3-12

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