基于分子中的原子量子理论分析锥形交叉点的稳定性及开环反应
发布时间：2021-02-03 05:32
一、QTAIM 简介量子力学通过假设状态函数包含了系统的一切,关注与物理性质相对应的可观测算子。在量子力学定理下,平均值（如维里定理）与Ehrenfest关系之间存在着相互关系。如果想要在量子力学的框架内发现化学,就应该找到一种确定系统各子系统可观测值的方法。此处,一个系统的子系统相当于分子中的原子。分子中的原子量子理论（QTAIM）是量子力学的广义表述,由Richard Bader教授从20世纪60年代早期发展而来,在过去的几十年中,QTAIM逐渐成为一种处理化学系统问题的理论。QTAIM恢复了分子结构假说的中心操作概念,即具有加和性和特性集的原子官能团,以及键合路径的定义,键合路径的存在是键存在的充分必要条件。QTAIM为仅使用电荷密度（或电子密度）分布ρ（r）的键合研究提供了一种有力的方法。分子的电子密度分布ρ（r）是用于研究分子系统的键合的本质。电子密度分布ρ（r）在空间中的原子核位置表现出极大值、极小值或鞍点、局部极大值。这三种点称为临界点（CPs）。总电子电荷密度分布ρ（r）的一阶导数在临界点处消失,即▽ρ（r）=0。电子密度分布ρ（r）在临界点处的任意坐标,存在九个二阶导...
【文章来源】：湖南师范大学湖南省 211工程院校
【文章页数】：138 页
【学位级别】：硕士
【文章目录】：
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
攻读硕士学位期间参与发表的论文
本文编号：3015983
【文章来源】：湖南师范大学湖南省 211工程院校
【文章页数】：138 页
【学位级别】：硕士
【文章目录】：
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
攻读硕士学位期间参与发表的论文
本文编号：3015983
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