基于分子中的原子量子理論分析錐形交叉點(diǎn)的穩(wěn)定性及開環(huán)反應(yīng)
發(fā)布時(shí)間：2021-02-03 05:32
一、QTAIM 簡(jiǎn)介量子力學(xué)通過假設(shè)狀態(tài)函數(shù)包含了系統(tǒng)的一切,關(guān)注與物理性質(zhì)相對(duì)應(yīng)的可觀測(cè)算子。在量子力學(xué)定理下,平均值（如維里定理）與Ehrenfest關(guān)系之間存在著相互關(guān)系。如果想要在量子力學(xué)的框架內(nèi)發(fā)現(xiàn)化學(xué),就應(yīng)該找到一種確定系統(tǒng)各子系統(tǒng)可觀測(cè)值的方法。此處,一個(gè)系統(tǒng)的子系統(tǒng)相當(dāng)于分子中的原子。分子中的原子量子理論（QTAIM）是量子力學(xué)的廣義表述,由Richard Bader教授從20世紀(jì)60年代早期發(fā)展而來,在過去的幾十年中,QTAIM逐漸成為一種處理化學(xué)系統(tǒng)問題的理論。QTAIM恢復(fù)了分子結(jié)構(gòu)假說的中心操作概念,即具有加和性和特性集的原子官能團(tuán),以及鍵合路徑的定義,鍵合路徑的存在是鍵存在的充分必要條件。QTAIM為僅使用電荷密度（或電子密度）分布ρ（r）的鍵合研究提供了一種有力的方法。分子的電子密度分布ρ（r）是用于研究分子系統(tǒng)的鍵合的本質(zhì)。電子密度分布ρ（r）在空間中的原子核位置表現(xiàn)出極大值、極小值或鞍點(diǎn)、局部極大值。這三種點(diǎn)稱為臨界點(diǎn)（CPs）�？傠娮与姾擅芏确植鸡眩╮）的一階導(dǎo)數(shù)在臨界點(diǎn)處消失,即▽?duì)眩╮）=0。電子密度分布ρ（r）在臨界點(diǎn)處的任意坐標(biāo),存在九個(gè)二階導(dǎo)...
【文章來源】：湖南師范大學(xué)湖南省 211工程院校
【文章頁數(shù)】：138 頁
【學(xué)位級(jí)別】：碩士
【文章目錄】：
摘要
ABSTRACT
Charpter 1.Theoretical Background and Computation Methodology
1.1 QTAIM Background
1.2 Four Type of Critical Points
1.3 Bond Path
1.4 The QTAIM and Stress Tensor BCP Properties
1.4.1 Ellipticity （ε）
1.4.2 Stiffness S and Polarizability P
b）"> 1.4.3 Metallicity ζ（rb）
1.4.4 Charge Shift Ratio Ε（rb）
b）"> 1.4.5 Total Local Energy Density H（rb）
1.4.6 Quantum Stress Tensor, σ（r）
1.4.7 Stress Tensor Ellipticity
1.5 The QTAIM and Stress Tensor Bond-Path Properties
1.5.1 The Bond-Path Length （BPL）and Bond-Path Curvature
1.5.2 The Bond-Path Framework Set, B={p,q,r}
*or H"> 1.5.3 The Eigenvector-Following Paths H*or H
σH={pσH,qσH,r}and Bσ={pσ,qσ,r}"> 1.5.4 The Stress Tensor Bond-Path Framework Set,BσH={pσH,qσH,r}and Bσ={pσ,qσ,r}
1.6 Density Functional Thoery
1.6.1 Introduction
1.6.2 The Spin-Restricted Ensemble-Referenced Kohn-Sham（REKS） Methodology
1.7 A Brief Introduction to Gaussian and AIMAll
Charpter 2.A 3-D Bonding Perspective of the Factors Influencing theRelative Stability of the S1/S0 Conical Intersections of thePenta-2,4-Dieniminium Cation（PSB3）
2.1 Introduction
2.2 Theory and Methods
b）"> 2.2.1 The QTAIM and Stress Tensor BCP Properties;Ellipticity ε,Total Local Energy Density H（rb）
*,H, and theBond-Path Framework Set B={p,q,r}"> 2.2.2 The QTAIM Bond-Path Properties; BPL, theEigenvector-Following Paths with Lengths H*,H, and theBond-Path Framework Set B={p,q,r}
2.3 Computational Details
2.4 Results and Discussions
2.4.1 A QTAIM BCP Analysis of the Torsional BCPs
2.4.2 QTAIM Bond-Path Analysis of the Torsion BCPs andMolecular Graphs
2.5 Conclusions
2.6 Supplementary Materials for PSB3
Charpter 3. Next-Generation Quantum Theory of Atoms in Molecules forthe Photochemical Ring-Opening Reactions of Oxirane
3.1 Introduction
3.2 Theory and Methods
b）, and Stress Tensor Eigenvalueλ3σ
3.2.1 The QTAIM and Stress Tensor BCP Properties;Ellipticity ε,Total Local Energy Density H（rb）, and Stress Tensor Eigenvalueλ3σ<0
0,1={p0,p1
,（q0, q1）,（r0,r1）}"> 3.2.2 The QTAIM Bond-Path Properties; BPL, theEigenvector-Following Paths and the Bond-Path Framework SetB0,1={p0,p1
,（q0, q1）,（r0,r1）}
3.3 Computational Details
3.4 Results and Discussions
0 and S1 States Minimum EnergyPathways of the Oxirane Ring-Opening Reaction"> 3.4.1 Analysis of the S0 and S1 States Minimum EnergyPathways of the Oxirane Ring-Opening Reaction
3.4.2 A QTAIM and Stress Tensor BCP Analysis of the OxiraneRing-Opening Reaction
3.4.3 A QTAIM 3-D Bond-Path Analysis of Three MEPs of theOxirane Ring-Opening Reaction
3.5 Conclusions
3.6 Supplementary Materials for Oxriane
Charpter 4. The Directional Bonding of[1.1.1]Propellane withNext-Generation QTAIM
4.1 Introduction
4.2 Theory and Methods
b）, Total Local Energy DensityH（rb） and Charge Shift Ratio （?）（rb）"> 4.2.1 The QTAIM BCP Properties;Ellipticity ε,Stiffness S,Polarizability P, Metallicity ζ（rb）, Total Local Energy DensityH（rb） and Charge Shift Ratio （?）（rb）
σ={pσ,qσ,r}"> 4.2.2 The QTAIM and Stress Tensor Bond-Path Properties;BPL,the Bond-Path Framework Set B={p,q,r}and Stress TensorBond-Path Framework Set, Bσ={pσ,qσ,r}
4.3 Computational Details
4.4 Results and Discussions
4.5 Conclusions
4.6 Supplementary Materials for[1.1.1]propellane
Charpter 5. Summary and Further Work
5.1 Summary
5.2 Further Work
References
Acknowledgements
攻讀碩士學(xué)位期間參與發(fā)表的論文
本文編號(hào)：3015983
【文章來源】：湖南師范大學(xué)湖南省 211工程院校
【文章頁數(shù)】：138 頁
【學(xué)位級(jí)別】：碩士
【文章目錄】：
摘要
ABSTRACT
Charpter 1.Theoretical Background and Computation Methodology
1.1 QTAIM Background
1.2 Four Type of Critical Points
1.3 Bond Path
1.4 The QTAIM and Stress Tensor BCP Properties
1.4.1 Ellipticity （ε）
1.4.2 Stiffness S and Polarizability P
b）"> 1.4.3 Metallicity ζ（rb）
1.4.4 Charge Shift Ratio Ε（rb）
b）"> 1.4.5 Total Local Energy Density H（rb）
1.4.6 Quantum Stress Tensor, σ（r）
1.4.7 Stress Tensor Ellipticity
1.5 The QTAIM and Stress Tensor Bond-Path Properties
1.5.1 The Bond-Path Length （BPL）and Bond-Path Curvature
1.5.2 The Bond-Path Framework Set, B={p,q,r}
*or H"> 1.5.3 The Eigenvector-Following Paths H*or H
σH={pσH,qσH,r}and Bσ={pσ,qσ,r}"> 1.5.4 The Stress Tensor Bond-Path Framework Set,BσH={pσH,qσH,r}and Bσ={pσ,qσ,r}
1.6 Density Functional Thoery
1.6.1 Introduction
1.6.2 The Spin-Restricted Ensemble-Referenced Kohn-Sham（REKS） Methodology
1.7 A Brief Introduction to Gaussian and AIMAll
Charpter 2.A 3-D Bonding Perspective of the Factors Influencing theRelative Stability of the S1/S0 Conical Intersections of thePenta-2,4-Dieniminium Cation（PSB3）
2.1 Introduction
2.2 Theory and Methods
b）"> 2.2.1 The QTAIM and Stress Tensor BCP Properties;Ellipticity ε,Total Local Energy Density H（rb）
*,H, and theBond-Path Framework Set B={p,q,r}"> 2.2.2 The QTAIM Bond-Path Properties; BPL, theEigenvector-Following Paths with Lengths H*,H, and theBond-Path Framework Set B={p,q,r}
2.3 Computational Details
2.4 Results and Discussions
2.4.1 A QTAIM BCP Analysis of the Torsional BCPs
2.4.2 QTAIM Bond-Path Analysis of the Torsion BCPs andMolecular Graphs
2.5 Conclusions
2.6 Supplementary Materials for PSB3
Charpter 3. Next-Generation Quantum Theory of Atoms in Molecules forthe Photochemical Ring-Opening Reactions of Oxirane
3.1 Introduction
3.2 Theory and Methods
b）, and Stress Tensor Eigenvalueλ3σ
3.2.1 The QTAIM and Stress Tensor BCP Properties;Ellipticity ε,Total Local Energy Density H（rb）, and Stress Tensor Eigenvalueλ3σ<0
0,1={p0,p1
,（q0, q1）,（r0,r1）}"> 3.2.2 The QTAIM Bond-Path Properties; BPL, theEigenvector-Following Paths and the Bond-Path Framework SetB0,1={p0,p1
,（q0, q1）,（r0,r1）}
3.3 Computational Details
3.4 Results and Discussions
0 and S1 States Minimum EnergyPathways of the Oxirane Ring-Opening Reaction"> 3.4.1 Analysis of the S0 and S1 States Minimum EnergyPathways of the Oxirane Ring-Opening Reaction
3.4.2 A QTAIM and Stress Tensor BCP Analysis of the OxiraneRing-Opening Reaction
3.4.3 A QTAIM 3-D Bond-Path Analysis of Three MEPs of theOxirane Ring-Opening Reaction
3.5 Conclusions
3.6 Supplementary Materials for Oxriane
Charpter 4. The Directional Bonding of[1.1.1]Propellane withNext-Generation QTAIM
4.1 Introduction
4.2 Theory and Methods
b）, Total Local Energy DensityH（rb） and Charge Shift Ratio （?）（rb）"> 4.2.1 The QTAIM BCP Properties;Ellipticity ε,Stiffness S,Polarizability P, Metallicity ζ（rb）, Total Local Energy DensityH（rb） and Charge Shift Ratio （?）（rb）
σ={pσ,qσ,r}"> 4.2.2 The QTAIM and Stress Tensor Bond-Path Properties;BPL,the Bond-Path Framework Set B={p,q,r}and Stress TensorBond-Path Framework Set, Bσ={pσ,qσ,r}
4.3 Computational Details
4.4 Results and Discussions
4.5 Conclusions
4.6 Supplementary Materials for[1.1.1]propellane
Charpter 5. Summary and Further Work
5.1 Summary
5.2 Further Work
References
Acknowledgements
攻讀碩士學(xué)位期間參與發(fā)表的論文
本文編號(hào)：3015983
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