臺灣博碩士論文加值系統

第一部份
　　本論文用B3LYP/6-311+G(d)和B3LYP/6-311+G(d,p)的方法，分別探討硼與二氧化碳，BO, BS, B2O2 + H2的反應機構，並比較各種反應路徑的能量與特性。
　　藉由G2M(MP2)//B3LYP/6-311+G(d)精確計算，研究B + CO2  BO + CO反應的位能曲面圖。反應最可能的途徑為B + CO2 (0 kcal/mol)  TS1 (19.2 kcal/mol) trans-BOCO (-25.1 kcal/mol) TS2 (-22.0 kcal/mol) BO + CO (-64.0 kcal/mol) OBCO (-75.6 kcal/mol)。這結果解釋了在matrix isolation實驗中，觀察到主要的反應產物為OBCO。這個分子是經由BO和CO重新結合而得。
　　藉由G2M(MP2)//B3LYP/6-311+G(d,p)精確計算，研究BO/H2, B2O2/H2和BS/H2系統的位能曲面圖。在BO + H2的反應中，B會先吸引氫分子中的一個氫原子，經過渡態（TS1）8.3 kcal/mol反應能障，形成OBH + H且放出熱量6.8 kcal/mol。在此反應中，也可進行BO + H2  cis-HBOH或是利用BO中的O端去抓取氫原子，然而這些反應路徑的能障皆很高，各為36.4 kcal/mol和42.7 kcal/mol。反應經過0.3 kcal/mol的能障後，使OBH + H生成OBH2（此為BO/H2系統中，最穩定的化合物）。OBH2能量低於trans-HBOH有2.5 kcal/mol，也低於cis-HBOH有4.2 kcal/mol。OBH2克服27.7 kcal/mol的能障後，可異構化成trans-HBOH；越過10.8 kcal/mol的能障，轉成cis-HBOH。BOH + H能重新結合成trans-HBOH和cis-HBOH且無能量障礙。在B + H2O反應中，反應物剛開始會形成一錯合物B-OH2，然後越過4.73 kcal/mol的能障後會消除一個氫原子而形成BOH + H或BO + H2且越過6.23 kcal/mol的能障後，會形成trans-H BOH。trans-H BOH最後會分解成OBH + H和一小部分的BO + H2。s-OBBO相較於d-BO對於氫氣的反應是較不易。但是，兩個BO反應且越過8.3 kcal/mol的能障後，會得到t-OBBO。t-OBBO容易與氫氣反應，生成OB + OBH2（經由中間物t-OBBH2O）只須4.4 kcal/mol；而生成OBBOH + H只須7.4 kcal/mol。BS/H2反應與BO/H2反應很相似。兩者最大的不同處，在於BS不能插入H2，而且SBH2位於一個較低的能量井（低於BS + H2有37.3 kcal/mol ），以及將H進行1,2-轉移不只形成trans-HBSH也可形成cis-HBSH。在B + H2S反應中，能形成比B-OH2強的錯合物B-SH2，且預期反應會較B + H2O更快進行。
第二部份
　　本論文以固態法製備具有三層鈦酸鈣結構的Nd1-xCaxBa2Cu3Oy與NdBa2-xCaxCu3Oy系列的超導樣品。所有樣品的Tc、正交係數皆隨取代量增加而減少。當psh為0.2時，Tc有最大值。從Rietveld分析的結果得知，在Nd1-xCaxBa2Cu3Oy系列中，Ca皆會填入R位置形成電洞摻雜效應；而RBa2-xCaxCu3Oy系列中，Ca會填入R位置和Ba位置，且迫使R3+填入Ba位置形成電洞充填效應。Tc的下降與沿著c軸方向的Cu(2)-Cu(2)距離的縮短有關。另外，由O-1s和Cu-2p3/2 的XANES吸收光譜得知，在Nd1-xCaxBa2Cu3Oy系列中，除了銅氧面上的電洞濃度會影響超導性之外，O(1)上的電洞濃度也會影響Tc。而NdBa2-xCaxCu3Oy系列中，隨著Ca取代量的增加，氧含量也會減少，而且結構會從正交晶相轉變為四方晶相。當O(4)、O(5)在基底平面均勻分佈時，會使得銅氧面的電洞濃度減少，造成超導性下降。

Part I
This thesis deals with the calculation of reaction mechanism of B + CO2; BO, BS, B2O2 + H2; AlO +2 NO by density functional theory at B3LYP/6-311+G(d) and B3LYP/6-311+G(d,p) level. To find the potential energy diagram of above molecules in the reaction and analyzed their relationships. There are three reactions we studied and they are rendered here.
　　Ab initio and density functional G2M(MP2)//B3LYP/6-311+G(d) calculations have been carried out to investigate the potential energy surface for the B + CO2  BO + CO reaction. The most favorable reaction pathway has been shown to be B + CO2 (0.0 kcal/mol)  TS1 (19.2 kcal/mol)  trans-BOCO (-25.1 kcal/mol)  TS2 (-22.0 kcal/mol)  BO + CO (-64.0 kcal/mol)  OBCO (-75.6 kcal/mol). The results explain observation of OBCO as the major reaction product in the earlier matrix isolation experiments, where this molecule was likely been produced through secondary recombination of the primary BO and CO products.
　　Potential energy surfaces of various reactions in the BO/H2, B2O2/H2, and BS/H2 systems have been studied at the G2M(MP2)//B3LYP/6-311+G(d,p) level of theory. The BO + H2 reaction is shown to proceed by abstraction of a hydrogen atom by B to produce OBH + H with the barrier and exothermicity of 8.3 and 6.8 kcal/mol, respectively. The reaction can also occur by 1, 2-insertion of BO into the H-H bond or by H abstraction by the O atom; however, the barriers for these channels are much higher, 36.4 and 42.7 kcal/mol, respectively. Via a low ~ 0.3 kcal/mol barrier, the OBH + H reaction produces the OBH2 radical, which is the most stable compound in the BO/H2 system and lies 15.9, 2.5, and 4.2 kcal/mol below BO + H2, trans-HBOH, and cis-HBOH, respectively. OBH2 can isomerize to trans-HBOH overcoming a barrier of 27.7 kcal/mol and the latter can rearrange to the cis conformer with a barrier of 10.8 kcal/mol. BOH and H can recombine and form cis- or trans-HBOH without barriers. In the B + H2O reaction, the reactants can first form a weakly bound B-H2O complex, which then can eliminate an H atom producing BOH + H or undergo insertion of B into an O-H bond giving trans-HBOH with barriers of 4.7 and 6.2 kcal/mol relative to the initial reactants, respectively, and trans-HBOH can eventually decompose to OBH + H and a minor amount of BO + H2. Singlet OBBO is shown to be much less reactive with respect to H2 than the BO monomer. Alternatively, after two BO recombine to form a triplet OBBO molecule over a moderate 8.3 kcal/mol barrier, t-OBBO can easily react with H2 producing either BO + OBH2 (via a t-OBBH2O intermediate) or OBBOH + H with barriers of 4.4 and 7.4 kcal/mol, respectively. The reactions in the BS/H2 system are shown to be similar to those for BO/H2, except that BS cannot insert into H2, SBH2 resides in a much deeper potential well (37.3 kcal/mol below BS + H2) and can rearrange both to trans- and cis-HBSH, the B-H2S complex is more strongly bound than B-H2O, and the B + H2S reaction is expected to be significantly faster than the reaction of B + H2O.
Part II
　　Two series of single phase triple-perovskite superconducting samples with nominal compositions of Nd1-xCaxBa2Cu3Oy and NdBa2-zCazCu3Oy are prepared by the solid state reaction method. For all the samples, both the Tc and the orthorhombicity of the unit cell decrease with increasing Ca content. The results of Rietveld analysis indicate that the Ca ions in the Nd1-xCaxBa2Cu3Oy series occupy R site causing a hole doping effect, whereas part of Ca ions in the NdBa2-zCazCu3Oy series occupy R site and push the same amount of Nd3+ ions into Ba site, causing a hole filling effect. It is also found that Tc decreases linearly with decreasing the distance of Cu(2)-Cu(2) along the c-axis. The O-1s and Cu-2p3/2 X-ray absorption near edge structure (XANES) show that both the holes in the CuO2 planes and on the apical oxygen sites have a significant effect on the superconductivity of Nd1-xCaxBa2Cu3Oy series in the overdoped region. In the NdBa2-xCaxCu3Oy series, the oxygen contents and orthorhombicity are decreased with increasing Ca content. The evening distribution of O(4) and O(5) in the basal plane leads to a reduction in the number of holes in the CuO2 planes and a decrease in Tc.

目 錄
頁次
中文摘要 I
英文摘要 III
目　　錄 V
表格索引 X
圖片索引　　　 　　　　　　　　 　　　　　　　　　　　　 X IV
第一章　理論研究簡介
1-1、化學熱力學 ………………………………………………… 1
　　 1-2、觸媒及催化反應之定義 …………………………………… 5
1-3、理論計算 …………………………………………………… 7
1-4、量子化學 ………………………………………………… 13
1-4-1、薛丁格方程式 …………………………………… 14
1-4-2、原子單位 ………………………………………… 17
1-4-3、波恩-歐本海莫近似法（Born-Oppenheimer）… 17
1-4-4、分子軌域理論（Molecular Orbital Theory）…20
第二章 計算軟體
2-1、套裝軟體 ………………………………………………… 23
2-2、量子近似法 ……………………………………………… 25
2-2-1、Hatree-Fock方程式 …………………………… 25
2-2-2、密度泛函理論（Density Functional Theory）30
2-2-3、B3LYP法 ………………………………………… 34
2-2-4、MP擾動理論 …………………………………… 35
2-2-5、高斯-1和高斯-2理論 ………………………… 37
2-3、基底函數組（Basis Set）……………………………… 40
　　　 2-3-1、最小基底函數STO-3G ………………………… 43
2-3-2、分裂價層的基底函數（Split-Valence Basis
Sets）…………………………………………… 45
2-3-3、極化函數（Polarization Function）……… 46
2-3-4、擴散函數（diffuse function）……………… 47
2-3-5、考慮相干的基底函數（Correlation Consistent
basis set）…………………………………… 48
第三章 硼原子與二氧化碳反應機構的理論研究
3-1、B + CO2反應機構簡介 ………………………………… 49
3-2、化學理論計算 …………………………………………… 50
3-3、B + CO2的結果與討論 ………………………………… 51
3-3-1、反應機構 ……………………………………… 52
3-4、B + CO2的結論 ………………………………………… 57
第四章 BO, BS, B2O2與氫氣反應機構的理論研究
4-1、BO, BS, B2O2 + H2反應機構簡介 …………………… 59
4-2、化學理論計算 …………………………………………… 60
4-3、BO, BS, B2O2 + H2的結果與討論 …………………… 61
4-3-1、BO + H2 B + H2O反應機制 …………………… 61
4-3-2、B + H2O反應 …………………………………… 67
4-3-3、在BO + H2 系統中的反應速率常數 ………… 69
4-3-4、B2O2 + H2反應 ………………………………… 72
4-3-5、BS + H2 B + H2S反應機制 …………………… 77
4-3-6、B + H2S反應機制 ……………………………… 83
4-3-7、不同物種的生程熱 …………………………… 83
4-4、BO, BS, B2O2 + H2結論 ……………………………… 84
第五章　超導研究的簡介
5-1、超導體歷史發展 ………………………………………… 88
　　 5-2、超導氧化物的結構 ……………………………………… 91
5-3、超導理論 ………………………………………………… 93
5-4、X光吸收光譜 …………………………………………… 96
　　 5-5、YBa2Cu3Oy高溫超導的O-1s 及Cu-2p3/2的吸收光譜 102
5-6、離子間的取代 ………………………………………… 105
5-7、氧含量與電洞濃度 …………………………………… 106
5-8、研究動機與目的 ……………………………………… 107
第六章 超導研究的實驗及分析
6-1、實驗 …………………………………………………… 109
6-1-1、試藥 …………………………………………… 109
6-1-2、樣品的製備 …………………………………… 110
6-2、樣品的物性測量 ……………………………………… 111
6-2-1、X光粉末繞射圖譜鑑定與計算 ……………… 111
6-2-2、Guin和Latt方法 ……………………………… 116
6-2-3、Rietveld精算法 ……………………………… 119
6-3、X光近緣吸收光譜實驗與分析 ………………………… 123
6-3-1、光束線與實驗裝置 …………………………… 124
6-3-2、數據的分析方法 ……………………………… 125
6-3-3、O-1s近緣吸收光譜 …………………………… 128
6-3-4、Cu-2p3/2近緣吸收光譜 ……………………… 128
6-4、導電度的測量 ………………………………………… 129
6-5、氧含量滴定分析 ……………………………………… 134
6-6、計算 psh 及 pch ……………………………………… 136
6-7、磁化率的測量 ………………………………………… 138
第七章 超導研究的結果與討論
7-1、單位晶胞參數（a、b和c）、體積與正交係數 ……… 140
7-2、Rietveld分析 ………………………………………… 145
7-3、氧含量、電洞濃度與超導溫度 ……………………… 169
7-4、超導性分析 …………………………………………… 183
7-5、X光吸收光譜 …………………………………………… 188
7-5-1、Nd1-xCaxBa2Cu3Oy的O-1s吸收光譜 ………… 188
7-5-2、Nd1-xCaxBa2Cu3Oy的Cu-2p3/2吸收光譜 …… 197
7-5-3、NdBa2-zCazCu3Oy的O-1s吸收光譜 ………… 198
7-5-4、NdBa2-zCazCu3Oy的Cu-2p3/2吸收光譜 …… 207
第八章 超導研究的結論 ……………………………………………… 212
參考文獻 ……………………………………………………………… 215
附錄 …………………………………………………………………… 227

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