Exploring Chemical Concepts Through Theory and Computation

Preface xv

Foreword xvii

10 Questions About Exploring Chemical Concepts Through Theory and Computation xix

1 Chemical Concepts from Molecular Orbital Theory 1
Feng Long Gu, Jincheng Yu, and Weitao Yang

1.1 Introduction 1

1.2 Molecular Orbital Theory 2

1.3 Canonical Molecular Orbitals 5

1.4 Frontier Molecular Orbital Theory 5

1.5 Localized Molecular Orbitals 6

1.6 Regularized Nonorthogonal Localized Molecular Orbitals 11

1.7 Molecular Orbitalets 15

2 Chemical Concepts from Ab Initio Valence Bond Theory 23
Chen Zhou, Fuming Ying, and Wei Wu

2.1 Introduction 23

2.2 Ab Initio Valence Bond Theory 24

2.3 Chemical Concepts in VB Theory 31

2.4 A Brief Guide to Perform VB Calculations 36

2.5 Concluding Remarks 38

3 Chemical Concepts from Conceptual Density Functional Theory 43
Frank De Proft

3.1 Introduction 43

3.2 The Fundamentals: Density Functional Theory (DFT) and Kohn-Sham DFT 46

3.3 The First Derivatives: The Electronic Chemical Potential and the Electron Density 48

3.4 The Second Derivatives: Chemical Hardness, Fukui Function, Linear Response Function, and Related Quantities 51

3.5 Perturbational Perspective of Chemical Reactivity 62

3.6 Conclusions 64

4 Chemical Concepts from Density-Based Approaches in Density Functional Theory 71
Dongbo Zhao, Xin He, Chunying Rong, and Shubin Liu

4.1 Introduction 71

4.2 Four Density-Based Frameworks 72

4.3 Applications of Density-Based Approaches 79

4.4 Concluding Remarks 94

5 Chemical Bonding 101
Sudip Pan and Gernot Frenking

5.1 Introduction 101

5.2 The Physical Mechanism of the Chemical Bond 103

5.3 Bonding Models 108

5.4 Bond Length and Bond Strength 111

5.5 Dative and Electron-Sharing Bonds 120

5.6 Polar Bonds 124

5.7 Atomic Partial Charges and Atomic Electronegativity 130

5.8 Chemical Bonding in Main-Group Compounds: N2, CO, BF, LiF 131

5.9 Chemical Bonding of the Heavier Main-Group Atoms 135

5.10 Chemical Bonding in Transition Metal Complexes: M(CO)n (M = Ni, Fe, Cr, Ti, Ca; n = 4 - 8) 143

5.11 Summary 146

6 Partial Charges 161
Tian Lu and Qinxue Chen

6.1 Concept of Partial Charge 161

6.2 Methods of Calculating Partial Charges 166

6.3 Partial Charges of Typical Molecules 176

6.4 Computer Codes for Evaluating Partial Charges 179

6.5 Concluding Remarks 180

7 Atoms in Molecules 189
Angel Martin Pendas, Evelio Francisco, Julen Munarriz, and Aurora Costales

7.1 Introduction 189

7.2 The Quantum Theory of Atoms in Molecules (QTAIM) 190

7.3 QTAIM Atoms as Open Quantum Systems 194

7.4 Interacting Quantum Atoms (IQA) 200

8 Effective Oxidation States Analysis 207
Pedro Salvador

8.1 The Concept of Oxidation State 207

8.2 Oxidation State is Not Related to the Partial Charge 208

8.3 The Molecular Orbital Picture of the Ionic Approximation 210

8.4 Spin-Resolved Effective Fragment Orbitals and Effective Oxidation States (EOS) Analysis 213

8.5 EOS Analysis from Different AIM Schemes 216

8.6 Summary 220

9 Aromaticity and Antiaromaticity 223
Yago Garcia-Rodeja and Miquel Sola

9.1 Definition of Aromaticity 223

9.2 Physical Foundation 224

9.3 Measures of Aromaticity 226

9.4 Rules of Aromaticity 233

9.5 Metallabenzenes and Related Compounds as an Example 239

10 Acidity and Basicity 251
Ranita Pal, Himangshu Mondal, and Pratim K. Chattaraj

10.1 Introduction 251

10.2 Definitions and Theories 252

10.3 CDFT-Based Reactivity Descriptors 257

10.4 CDFT-Based Electronic Structure Principles 259

10.5 Systemics of Lewis Acid-Base Reactions: Drago-Wayland Equation 261

10.6 Strengths of Acid and Bases 262

10.7 Effect of External Perturbation 267

10.8 CDFT and Acidity 270

10.9 CDFT and ITA 272

10.10 Are Strong Bronsted Acids Necessarily Strong Lewis Acids? 276

10.11 Summary 278

11 Sigma Hole Supported Interactions: Qualitative Features, Various Incarnations, and Disputations 285
Kelling J. Donald

11.1 Introduction 285

11.2 Many Incarnations and Roles of a Single Phenomenon 288

11.3 Related Interactions Elsewhere in the Main Group 304

11.4 Contested Interpretations 308

11.5 Conclusions 308

12 On the Generalization of Marcus Theory for Two-State Photophysical Processes 317
Chao-Ping Hsu and Chou-Hsun Yang

12.1 Introduction 317

12.2 The Golden Rule Rate Expression 318

12.3 Application 325

12.4 Conclusion 330

13 Computational Modeling of CO2 Reduction and Conversion via Heterogeneous and Homogeneous Catalysis 335
Yue Zhang, Lin Zhang, Denghui Ma, Xinrui Cao, and Zexing Cao

13.1 Introduction 335

13.2 Computational Methods 336

13.3 Activation and Reduction of CO2 338

13.4 Catalytic Coupling of CO2 with CH4 345

13.5 Homogeneous Catalytic Conversion of CO2 348

13.6 Conclusion and Outlook 352

14 Excited States in Conceptual DFT 361
Frederic Guegan, Guillaume Hoffmann, Henry Chermette, and Christophe Morell

14.1 Introduction 361

14.2 Exploring Ground State Properties Thanks to Excited States 361

14.3 Exploring the Reactivity of Excited States with Excited States 371

14.4 Conclusion 375

15 Modeling the Photophysical Processes of Organic Molecular Aggregates with Inclusion of Intermolecular Interactions and Vibronic Couplings 379
WanZhen Liang, Yu-Chen Wang, Shishi Feng, and Yi Zhao

15.1 Introduction 379

15.2 Theoretical Approaches 381

15.3 Concluding Remarks 397

16 Duality of Conjugated Π Electrons 407
Yirong Mo

16.1 Introduction 407

16.2 The New Concept of Intramolecular Multibond Strain 412

16.3 Theoretical Method 413

16.4 Computational Analysis of the Concept of Intramolecular Multibond Strain 416

16.5 Experimental Evidence 422

16.6 Summary 426

17 Energy Decomposition Analysis and Its Applications 433
Peifeng Su

17.1 Introduction 433

17.2 Methodology 437

17.3 Applications of GKS-EDA 442

17.4 Conclusion 450

18 Chemical Concepts in Solids 455
Peter C. Muller, David Schnieders, and Richard Dronskowski

18.1 The Three Schisms of Solid-State Chemistry 455

18.2 Bloch’s Theorem 457

18.3 Basis Sets 460

18.4 Interpretational Tools 462

18.5 Applications 470

18.6 Summary 477

19 Toward Interpretable Machine Learning Models for Predicting Spectroscopy, Catalysis, and Reactions 481
Jun Jiang and Shubin Liu

19.1 Introduction 481

19.2 ML in a Nutshell 481

19.3 Chemistry-Based Descriptors as ML Features 485

19.4 Selected ML Applications 493

19.5 Concluding Remarks 507

20 Learning Design Rules for Catalysts Through Computational Chemistry and Machine Learning 513
Aditya Nandy and Heather J. Kulik

20.1 Computational Catalysis 513

20.2 Machine Learning (ML) in Catalysis 529

20.3 Summary 545

References 546

Index 559