臺灣博碩士論文加值系統

本研究以MP2、Hartree-Fock(HF) 近似計算，分析He ~ Kr原子的intracule 電子密度、extracule電子密度及一般電子密度的訊息。並且對一些簡單分子的intracule電子密度 I(R) 和extracule電子密度E(R) 進行計算，並分析它們的拓撲分佈。對分子的 I(R) 和 E(R) 的電子密度分佈的計算主要是採用Hartree-Fock (HF) 近似。對一些環烯平面分子計算的結果顯示了 I(R) 和 E(R) 的極大值位置和性質可以從原子核的相對位置來推測。 I(R) 的極大值來自於原子核附近的電子分佈以及不同原子核附近的相對電子分佈的極大值。 E(R) 的極大值來自同一原子核附近的電子分佈以及不同原子核中間的電子密度分佈極大值。

In this thesis Hartree-Fock (HF) approximation and MP2 method are used to calculate and analyze the electron intracule densities, extracule densities and normal densities of atoms. Some simple molecular topologies of the electron intracule densities and extracule densities, I(R) and E(R), are also calculated by HF method and analyzed. These topologies are found to be inherently more complex than those of the one-electron density. The main topological features of I(R) and E(R) are already present in the densities calculated within the Hartree-Fock (HF) approximation compare with those from correlated wave functions. Results of calculations on several planar molecules show that the positions, number and properties of attractors in I(R) and E(R) are predicted with a surprising fidelity by a native independent-atom model, making it possible to index distinct types of electron pairs present in atoms and molecules. The attractors in I(R) stem from electron pairs of both individual atoms and atomic pairs in the relative electron coordinate; the attractors in E(R) stem from both individual atoms and atomic pairs in the center of electron pair coordinate. The contributions to attractors by such light atom as hydrogen may be present or may not, depending on the other nuclei in the molecular system.

摘要 ……………………………………………………………III
Abstract IV
圖目錄 VII
表目錄 XVI
第壹章 序論 1
第貳章 原理與計算方法 5
2-1 前言 5
2-2 基本理論 6
2-2-1 波恩-奧本海默近似 (Born-Oppenheimer approximation)1,2 6
2-2-2 SCF 運算程序 9
2-2-3 變分法（Variation Method） 10
2-3 基底函數（Basis Function） 12
2-4 計算方法 18
2-4-1 Hartree Fock 方法 18
2-4-2 Møller Plesset方法1,2,3,4 24
2-5 電算方法2,4 37
2-5-1 單點計算（single point calculation） 38
2-5-2 幾何優選（geometry optimization） 39
2-5-3 簡諧頻率計算 40
第參章 原子的性質 42
3-0 前言 42
3-1 以MP2/aug-cc-pV5Z計算原子的intracule density, extracule density 和電子密度 42
3-2 以HF/6-31G*方法計算原子的intracule density, extracule density 與電子密度 46
3-3 Extracule density 和intracule density 的比值 52
3-4 原子熱力學性質與電子密度的關係 54
第肆章 含氫雙原子分子的電子密度 68
4-1 氫在intracule density與extracule density的訊號 68
4-2 X-H鍵在intracule density與extracule density的訊號 71
第伍章 簡單碳氫化合物的Intracule density 103
5-1 前言 103
5-2 簡單分子的intracule density訊號 104
5-2-1 CH的intracule density訊號 104
5-2-2 C2的intracule density訊號 105
5-2-3 CH4的intracule density訊號 108
5-2-4 C2H2的intracule density訊號 109
5-2-5 C2H4的intracule density訊號 111
第陸章 簡單碳氫化合物的Extracule density 116
6-1 前言 116
6-2 簡單的碳氫化合物extracule density訊號 117
6-2-1 CH的extracule density訊號 117
6-2-2 C2的extracule density訊號 120
6-2-3 CH4的extracule density訊號 123
6-2-4 C2H2的extracule density訊號 124
6-2-5 C2H4的extracule density訊號 126
6-2-6 C2H6的extracule density訊號 129
第柒章 平面環烯分子的計算 131
7-0 前言 131
7-1 環丁二烯的計算 131
7-1-1 環丁二烯的intracule density計算 131
7-1-2 環丁二烯的extracule density計算 134
7-2 苯的計算 136
7-2-1 苯的intracule density計算 136
7-2-2 苯的extracule density計算 139
第捌章 Fukui function f (r)的應用 142
8-1 計算環丁二烯的Fukui function 20,21,22,23,24 142
陰離子相應的 Fukui function f (r) 如下， 142
8-2 用環丁二烯的intracule density及extracule density計算Fukui function 144
8-2-1 環丁二烯的fI (r)、fE (r)計算 144
第玖章 結論 153
參考資料 157

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