# Exploring Chemical Concepts Through Theory and Computation

By: Shubin Liu (Editor)

Hardcover | 26 August 2024 | Edition Number 1

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592 Pages

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**Exploring Chemical Concepts Through Theory and Computation**

**Deep, theoretical resource on the essence of chemistry, explaining a variety of important concepts including redox states and bond types**

*Exploring Chemical Concepts Through Theory and Computation *provides a comprehensive account of how the three widely used theoretical frameworks of valence bond theory, molecular orbital theory, and density functional theory, along with a variety of important chemical concepts, can between them describe and efficiently and reliably predict key chemical parameters and phenomena. By comparing the three main theoretical frameworks, readers will become competent in choosing the right modeling approach for their task.

The authors go beyond a simple comparison of existing algorithms to show how data-driven theories can explain why chemical compounds behave the way they do, thus promoting a deeper understanding of the essence of chemistry. The text is contributed to by top theoretical and computational chemists who have turned computational chemistry into today's data-driven and application-oriented science.

*Exploring Chemical Concepts Through Theory and Computation *discusses topics including:

- Orbital-based approaches, density-based approaches, chemical bonding, partial charges, atoms in molecules, oxidation states, aromaticity and antiaromaticity, and acidity and basicity
- Electronegativity, hardness, softness, HSAB, sigma-hole interactions, charge transport and energy transfer, and homogeneous and heterogeneous catalysis
- Electrophilicity, nucleophilicity, cooperativity, frustration, homochirality, and energy decomposition
- Chemical concepts in solids, excited states, spectroscopy and machine learning, and catalysis and machine learning, as well as key connections between related concepts

Aimed at both novice and experienced computational, theoretical, and physical chemists, *Exploring Chemical Concepts Through Theory and Computation *is an essential reference to gain a deeper, more advanced holistic understanding of the field of chemistry as a whole.

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

ISBN: 9783527352487

ISBN-10: 3527352481

Available: 26th August 2024

Format: Hardcover

Language: English

Number of Pages: 592

Audience: Professional and Scholarly

Publisher: Wiley-VCH

Country of Publication: DE

Edition Number: 1

Dimensions (cm): 24.41 x 16.99 x 15.0

Weight (kg): 0.67

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