Putz / Cimpoesu / Ferbinteanu Structural Chemistry

Principles, Methods, and Case Studies
1. Auflage 2018
ISBN: 978-3-319-55875-2
Verlag: Springer Nature Switzerland
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 825 Seiten

This book explains key concepts in theoretical chemistry and explores practical applications in structural chemistry. For experimentalists, it highlights concepts that explain the underlying mechanisms of observed phenomena, and at the same time provides theoreticians with explanations of the principles and techniques that are important in property design. Themes covered include conceptual and applied wave functions and density functional theory (DFT) methods, electronegativity and hard and soft (Lewis) acid and base (HSAB) concepts, hybridization and aromaticity, molecular magnetism, spin transition and thermochromism. Offering insights into designing new properties in advanced functional materials, it is a valuable resource for undergraduates of physical chemistry, cluster chemistry and structure/reactivity courses as well as graduates and researchers in the fields of physical chemistry, chemical modeling and functional materials.


Mihai V. Putz is currently an Associate Professor of theoretical and computational physical chemistry at the West University of Timisoara, Romania. He has an interdisciplinary training and research experience in physics, chemistry and spectroscopy and has been involved in numerous postdoctoral projects at the University of Calabria, Italy and in the Free University of Berlin, Germany. He has made valuable contributions to computational, quantum, and physical chemistry through seminal works published in numerous international journals. He is also a member of many professional societies and has received several national and international awards. In 2010 Mihai V. Putz was declared through a national competition the Best Researcher of Romania, while in 2013 he was recognized among the first Dr.-Habil. in Chemistry in Romania. From 2014 he became a full member of International Academy of Mathematical Chemistry.
Fanica Cimpoesu graduated from the University of Bucharest. His PhD work, under the guidance of I. B. Bersuker, was dedicated to the orbital models of vibronic effects. Self-didactically, he approached several other topics such as organometallic stereochemistry and molecular magnetism, continuously enlarging his research area. The trademark of Fanica Cimpoesu's work is finding new methodological clues and heuristic viewpoints at the borderline between theory, computation and experimental chemistry. Research stages at the universities of Leuven (Prof. A. Ceulemans), Tokyo (Prof. K. Hirao) and Fribourg (Prof. C. A. Daul) are acknowledged as emulative events in his curriculum vitae.
Marilena Ferbinteanu is an Associate professor at the University of Bucharest, Faculty of Chemistry, Inorganic Chemistry Department. She graduated and received her MS, PhD degrees in inorganic chemistry, at the same university. In 1999 she was awarded with the Alexander Von Humboldt fellowship (Prof. Herbert Roesky) and in 2004 with the Japan Society for Promotion Science fellowship (Prof. Masahiro Yamashita). She had several postdoctoral stages in Germany (Institute of Inorganic Chemistry, Göttingen, 2001) and in Japan (Ochanomizu University, Prof. Yutaka Fukuda, 2002; Tokyo Metropolitan University, Prof. Masahiro Yamashita and Hitoshi Miyasaka, 2003). In 2010 she won the first UEFISCDI-PCCE grant competition. She promoted advanced structural-property correlations combining the experiment, structural and applied coordinative chemistry, magnetic and optic properties with theory.

Autoren/Hrsg.

Putz, Mihai V.

Cimpoesu, Fanica

Ferbinteanu, Marilena

Inhaltsverzeichnis

1;Foreword I;5
2;Foreword II;5
3;Preface;11
4;Acknowledgements;18
5;Contents;19
6;About the Authors;27
7;1 Atomic Structure and Quantum Mechanics;29
7.1;Abstract;29
7.2;1.1 The Long Road from Democritus to Bohr;30
7.2.1;1.1.1 Arcadian Antiquity;30
7.2.2;1.1.2 Along the Centuries, to the Positivist Era;32
7.2.3;1.1.3 Bohr’s Atomic Model: Natura Facit Saltus!;33
7.3;1.2 The Dawn of Quantum Theory and the Founding Fathers;39
7.3.1;1.2.1 The Revolutionary Milieu and Quantum Mechanics;39
7.3.2;1.2.2 Modus Operandi: Waves and Operators;40
7.3.3;1.2.3 The Schrödinger Equation and Schrödinger’s Cat;45
7.3.4;1.2.4 The Heisenberg Equations: Uncertainty and Matrix Mechanics;47
7.3.5;1.2.5 Hamiltonian Matrices, Non-orthogonal Bases, Variational Methods;51
7.4;1.3 Atomic Shell Structure and the Spherical Harmonics;55
7.4.1;1.3.1 Atomic Orbitals and Quantum Numbers: The Radial-Angular Factorization of the Atomic Wave Functions;55
7.4.2;1.3.2 Intuitive Primer on the Pattern of Atomic Orbitals;57
7.4.3;1.3.3 Toward Setting the Schrödinger Equation in Atoms;62
7.4.4;1.3.4 The Schrödinger Equation for the One-Electron Atom: The Radial Part;64
7.4.5;1.3.5 A Qualitative Analysis of the Radial Nodal Structure of the Atomic Orbitals;68
7.4.6;1.3.6 The Complete Analytic Formulas of the Atomic Orbitals;70
7.4.7;1.3.7 A Philosophical Divagation;72
7.5;1.4 Elements of Relativistic Quantum Mechanics;73
7.5.1;1.4.1 The Electronic Spin, the Missing Link Between Atomic Shell Scheme and Chemical Systematics from the Periodic Table of Elements;73
7.5.2;1.4.2 First Principles of Relativistic Quantum Mechanics: Klein-Gordon and Dirac Equations;77
7.5.3;1.4.3 The Quantum Numbers of Dirac Relativistic Equations;80
7.5.4;1.4.4 The Two Quantum Worlds of Dirac Equations: Small and Large Spinor Components;81
7.5.5;1.4.5 Toward the Relativistic Atom: Electromagnetism Instead of Electrostatics;83
7.5.6;1.4.6 Concluding the Types of Relativistic Hamiltonian Terms: Zeeman, Spin–Orbit, Mass-Correction, Darwin, Breit, Breit-Pauli;86
7.5.7;1.4.7 The Spin–Orbit Coupling: A Term to Remember;88
7.6;1.5 Perturbation Theory Application: Quantum Polarizability;93
7.7;1.6 Atomic Stability: The Proof by Quantum Path Integrals;103
7.7.1;1.6.1 Schrodinger Equation by Quantum Path Integral;103
7.7.2;1.6.2 Feynman-Kleinert Effective Density Formalism;107
7.7.3;1.6.3 Quantum Smeared Effects and the Stability of Matter;112
7.7.4;1.6.4 Ground State (? ? ?, T ? 0 K) Case;118
7.8;1.7 Free and Observed Quantum Evolution: Extended Heisenberg Uncertainly Relationship (HUR) by Path Integrals;121
7.8.1;1.7.1 HUR by Periodic Paths;122
7.8.2;1.7.2 Wave-Particle Ratio Function;125
7.8.3;1.7.3 Extended HUR;127
7.9;1.8 Conclusions;131
7.10;References;132
8;2 Wave Function Theories and Electronic Structure Methods: Quantum Chemistry, from Atoms to Molecules;135
8.1;Abstract;135
8.2;2.1 Poly-electronic Wave Functions from Spin-Orbitals;136
8.2.1;2.1.1 Indiscernible Electrons and Anti-symmetric Wave Functions with Slater Determinants;136
8.2.2;2.1.2 Matrix Elements in a Basis of Slater Determinants: The Slater Rules;141
8.2.3;2.1.3 The Atomic Integrals: The Slater–Condon Symmetry Factorization of the Two-Electron Integrals;147
8.2.4;2.1.4 Orbital and Spin Quantum Numbers in the Poly-electronic Atom: The Spectral Terms;150
8.2.5;2.1.5 Slater Rules at Work: A Hands-On Example on the Helium Atom;157
8.3;2.2 Atoms with Many Electrons: A Guided Tour Through Selected Examples;165
8.3.1;2.2.1 Spectral Terms of Main Group Elements: The Li, B, C, N, O, F, Ne Series;165
8.3.2;2.2.2 Spectral Terms of Transition Metal Ions;172
8.3.3;2.2.3 Other Notes: Racah Parameters for Real-Type d Orbitals. Calculation of Slater–Condon Parameters. Approximate Ratios in the Series of Slater–Condon or Racah Parameters;176
8.4;2.3 Atomic Spectra in Practical Applications: From Neon Tubes to Warm White Light;180
8.4.1;2.3.1 Fiat Lux! Sunlight and Black Body Radiation;180
8.4.2;2.3.2 Generating Light from Atoms Excited in Plasma;181
8.4.3;2.3.3 Converting the Light Wavelength with Solid-State Phosphors;185
8.5;2.4 Back to the Basis! Atomic Basis Sets: Slater versus Gaussian Orbitals and Other Options;190
8.5.1;2.4.1 Deconstructing the Hydrogen-Type Analytic Atomic Orbitals and Recomposing the One-Electron Atom from Slater-Type Primitives;190
8.5.2;2.4.2 A Test with Slater-Type Orbitals (STOs);198
8.5.3;2.4.3 The Gaussian-Type Orbitals (GTOs): The “Steel and Concrete” of the Massive Development of Quantum Chemistry;200
8.5.4;2.4.4 Caveats on Gaussian-Type Basis Sets;208
8.5.5;2.4.5 Other Options: Plane Waves and Numerical Bases;214
8.6;2.5 Ab Initio Methods;222
8.6.1;2.5.1 Hartree–Fock Method: The Simplest Level of Electronic Structure Calculations in Atoms and Molecules;222
8.6.2;2.5.2 Multi-configuration Self-consistent Field Methods: Closer to the Physical Truth and Chemical Realism;228
8.6.3;2.5.3 Valence Bond: A Tribute to the Historical Roots of Bond Theories and Yet a Promising Land;236
8.7;2.6 Conclusions;243
8.8;References;244
9;3 Density Functional Theory: From Conceptual Level Toward Practical Functionality;249
9.1;Abstract;249
9.2;3.1 Background and Principles;250
9.2.1;3.1.1 The Deep Roots of Density Functional Theory;250
9.2.2;3.1.2 The Hohenberg–Kohn Theorems and the Problem of Universals in Electronic Structure;251
9.2.3;3.1.3 A Bit of Maieutics on Exchange and Correlation Holes;255
9.2.4;3.1.4 An Illustration of Density Functional Issues;258
9.2.5;3.1.5 Methods and Concepts in DFT: Kohn–Sham Self-consistent Field, Fractional Occupations, Electronegativity and Chemical Hardness (Electrorigidity);262
9.2.6;3.1.6 The Chemical Relevance of DFT: Electronegativity Equalization, Maximum Hardness Principle, Hard and Soft Acids and Bases (HSAB);266
9.2.7;3.1.7 Ways to Approximated Density Functionals;269
9.2.8;3.1.8 Other Issues Related to Density Functional Theory: The DFT+U Methods and an Atomic Model Based on the Interpolation of Spectroscopic Configuration Energies;276
9.2.9;3.1.9 A Phenomenological Model: Energy of Atoms as Continuous Function of Valence Shell Populations;282
9.3;3.2 Density Functional Theory in More Detail;294
9.3.1;3.2.1 Density Functionals of Kinetic Energy;294
9.3.2;3.2.2 Density Functionals of Exchange Energy;297
9.3.3;3.2.3 Density Functionals of Correlation Energy;302
9.3.4;3.2.4 Density Functionals of Exchange-Correlation Energy;308
9.4;3.3 Conclusions;312
9.5;References;313
10;4 Bond! Chemical Bond: Electronic Structure Methods at Work;318
10.1;Abstract;318
10.2;4.1 Molecular Structure by Computational Chemistry: A Brief Synopsis;320
10.3;4.2 Hartree–Fock Versus Density Functional Theory Computation Simple Samples;324
10.4;4.3 Orbitals, the Building Blocks of Electronic Structure;331
10.5;4.4 The H2 Molecule: The Simplest Bond Prototype. Phenomenological Models and Calculation Methods;336
10.5.1;4.4.1 The Spin-Coupling Phenomenology of the Chemical Bond;336
10.5.2;4.4.2 Model Calculations on H2;340
10.6;4.5 Computational and Conceptual Valence Bond: The Spin Coupling Paradigm at Work;350
10.6.1;4.5.1 Overture to the Valence Bond Calculations;350
10.6.2;4.5.2 Benzene: Valence Bond Versus Complete Active Space;352
10.6.3;4.5.3 Playing with Graphic Rules for Setting a VB Modeling;359
10.7;4.6 Mobilis in Mobile: Electrons Moving Around Mobile Nuclei. Floppy Molecules, Unstable Systems, and Chemical Reactions;368
10.7.1;4.6.1 Jahn–Teller and Related Effects. Vibronic Coupling;368
10.7.2;4.6.2 A Simple Approach of the H3 Prototypic System. Example for Reaction Potential Energy Surfaces and E ? E-Type Jahn–Teller Effect;371
10.7.3;4.6.3 The Computational Approach of the Pseudo Jahn–Teller Effect (Second-Order Vibronic Coupling);378
10.7.4;4.6.4 The Vibronic Orbitals;384
10.7.5;4.6.5 More on the Usage of Vibronic Modeling;389
10.7.5.1;4.6.5.1 Two State Models of Pseudo Jahn–Teller Effect;389
10.7.5.2;4.6.5.2 Vibronic Phenomenology of Mixed Valence Systems;392
10.7.5.3;4.6.5.3 The Use of Vibronic Models to Fit Potential Energy Curves, Surfaces and Hyper-Surfaces;395
10.8;4.7 Breaking Symmetry in Quantum Chemistry;400
10.8.1;4.7.1 The Symmetry Breaking of Chemical Field Generation;400
10.8.2;4.7.2 The Inverse Quantum Chemical Problem;404
10.9;4.8 Conclusions;409
10.10;References;411
11;5 New Keys for Old Keywords: Hybridization and Aromaticity, Graphs and Topology;416
11.1;Abstract;416
11.2;5.1 Introduction;417
11.3;5.2 The Concept of Hybridization;418
11.3.1;5.2.1 Hybrids with s and p Orbitals: A Good Basis of Discussion;418
11.3.2;5.2.2 The Natural Hybrids Orbitals from Natural Bond Orbital Analysis of Electronic Density;423
11.3.3;5.2.3 Are the Hybrids with s, p, and d Composition Realistic?;426
11.3.4;5.2.4 Hybrids in the Isolobal Analogy;430
11.4;5.3 Aromaticity as Resonance;435
11.4.1;5.3.1 Criteria of Aromaticity;435
11.4.2;5.3.2 Iconic Prototypes: Aromaticity in Benzene Versus Anti-aromaticity in Cyclobutadiene, from Valence Bond Perspective;438
11.4.3;5.3.3 Resonance Structures Without a Valence Bond Frame;450
11.4.4;5.3.4 The Spherical Aromaticity in Inorganic Clusters: The Icosahedral Borane;456
11.4.5;5.3.5 Aromaticity and Anti-aromaticity in Non-organic Systems;460
11.5;5.4 Aromaticity by Chemical Reactivity;463
11.5.1;5.4.1 Modeling Molecular Aromaticity with Electronegativity and Chemical Hardness;463
11.5.2;5.4.2 Modeling Absolute Aromaticity of Atoms-in-Molecules;467
11.5.3;5.4.3 Modeling Compact Aromaticity of Atoms-in-Molecules;474
11.6;5.5 Chemical Bonding by Coloring Reactivity;491
11.6.1;5.5.1 Reactivity Coloring of Topological Distance Matrix;491
11.6.2;5.5.2 Reactivity Coloring of Topological Adjacency Matrix;502
11.7;5.6 Conclusions;521
11.8;References;522
12;6 Coordination Bonding: Electronic Structure and Properties;529
12.1;Abstract;529
12.2;6.1 The Ligand Field Theory: An Evergreen Field;530
12.2.1;6.1.1 The Puzzle of Supra-valent Coordination Numbers and Werner’s Clear Cut Theory;530
12.2.2;6.1.2 Generalities on Ligand Field Modeling;531
12.2.3;6.1.3 The Effective Electrostatic Formalism of Ligand Field Theory;534
12.2.4;6.1.4 The General Formulation of the Ligand Field Potential in Spherical Harmonics Basis;536
12.2.5;6.1.5 Particular Ligand Field Hamiltonians in Selected Symmetries;541
12.2.6;6.1.6 Limitations of Ligand Field Modeling: The Holohedrization Effect;548
12.2.7;6.1.7 Ligand Field Potential Maps: A Picturesque Representation of Multi-parametric Systems;552
12.3;6.2 The Angular Overlap Model (AOM): Angling for Chemical Meaning in Ligand Field Parameterization;555
12.3.1;6.2.1 Principles and Techniques of AOM: Chemists Believe in Orbital Overlapping;555
12.3.2;6.2.2 The AOM Parameterization in Prototypic Cases;559
12.3.3;6.2.3 Meaning and Estimation of AOM Parameters;561
12.4;6.3 Bonding Schemes and Ligand Field Stabilization Energy in Transition Metal Complexes;565
12.5;6.4 Modeling  Electronic Spectroscopy of Transition Metal Complexes;569
12.5.1;6.4.1 Taking a Case Study: The [Ni(Phen)3]2+ Complex. Preamble: Molecular Geometry of the Complex Electronic Structure of the Free Metal Ions;569
12.5.2;6.4.2 Calculation of the Ligand Field Spectra by Multi-configuration Methods;571
12.5.3;6.4.3 The Advanced Level: Guiding the Calculations and Handling the Results to Meet the Ligand Field Phenomenology;573
12.5.4;6.4.4 The Time Dependent Density Functional Theory (TD-DFT) Calculation of Electronic Spectra in Coordination Compounds: Limitations and Advantages;584
12.6;6.5 The Thermochromism of Coordination Compounds;590
12.6.1;6.5.1 A Colorful Topic;590
12.6.2;6.5.2 Thermochromic Behavior by Linkage Isomerism: The Nitro-nitrito Isomerization;592
12.6.3;6.5.3 The Thermochromism of the Tetrahalocuprates: Tetrahedral-Square Planar Switching;597
12.7;6.6 The Specifics and Subtleties of the Electronic Structure of Lanthanide Complexes. Ligand Field + Spin-Orbit = Magnetic Anisotropy;611
12.7.1;6.6.1 The Puzzle of the f Orbitals in Molecule;611
12.7.2;6.6.2 An Intermezzo on Magnetic Anisotropy;612
12.7.3;6.6.3 The Non-aufbau Nature of the f-Shell in the Molecular Orbital Pictures;614
12.7.4;6.6.4 The Multi-configurational Methods of the f-Element Complexes: The First-Principles Route to Ligand Field Phenomenology and ab initio Magnetic Anisotropy;616
12.7.5;6.6.5 Other Ways of LF Modeling: Stevens Equivalent Operators Technique, Exemplified in Axial Symmetry;627
12.8;6.7 Conclusions;632
12.9;References;634
13;7 The Modeling in Molecular Magnetism;639
13.1;Abstract;639
13.2;7.1 Phenomenological Models in Magnetochemistry;641
13.2.1;7.1.1 The Spin Coupling Hamiltonian;641
13.2.2;7.1.2 Other Effective Magnetic Components: Zeeman Hamiltonian and Zero Field Splitting;643
13.2.3;7.1.3 Magnetic Susceptibility;645
13.3;7.2 Fit to Experiment of Spin Coupling Parameters: Some Non-trivial Issues;648
13.4;7.3 The CASSCF and Broken Symmetry DFT Methods, Face to Face, in the Estimation of Exchange Coupling Parameters;652
13.5;7.4 The Broken Symmetry Approach to Poly-nuclear Systems;655
13.6;7.5 The Complexity of Structure-Property Relationships Poly-nuclear Systems Within Lanthanide Ions: Spin Coupling, Ligand Field, and Spin-Orbit Factors;659
13.6.1;7.5.1 Generic Mechanisms for Ferromagnetic and Antiferromagnetic d-f Exchange Couplings. The Case of Cu–Gd Complexes;659
13.6.2;7.5.2 Exchange Coupling in d-f Complexes with Degenerate Ground Terms of Lanthanide Ions;664
13.6.3;7.5.3 The Ligand Field Analysis of the CASSCF Results;667
13.6.4;7.5.4 The Angular Overlap Modeling of the Ligand Field in Lanthanide Complexes;672
13.6.5;7.5.5 Magnetic Anisotropy of the Lanthanide Ions in Ground and Excited States. State-Specific Magnetization Polar Maps. The Ab Initio Simulation of the Magnetic Properties;674
13.7;7.6 The Spin Crossover Phenomena;682
13.7.1;7.6.1 Generalities;682
13.7.2;7.6.2 A Simple Modeling of the Ligand Field Versus Spin Coupling Balance;684
13.7.3;7.6.3 Adding the Vibrational Factors;688
13.7.4;7.6.4 Illustration of the Spin Crossover in Prototypic Fe(II) Complexes;691
13.7.5;7.6.5 The Rare Cases of Spin Crossover in Mn(III) Complexes;696
13.8;7.7 Conclusions;700
13.9;References;702
14;8 Bonding in Rings and Clusters;706
14.1;Abstract;706
14.2;8.1 Clues for Heuristic Insight in the Structure of Quasi-symmetric Systems;707
14.2.1;8.1.1 Symmetry as Ancillary Tool;707
14.2.2;8.1.2 Point Groups in a Nutshell;708
14.2.3;8.1.3 Orbital Symmetry in Ring Systems;711
14.3;8.2 Tensor Surface Harmonics (TSH) Theory;714
14.3.1;8.2.1 Orbital Patterns in Quasi-spherical Clusters;714
14.3.2;8.2.2 Modeling Clusters by Vector Surface Harmonics;729
14.3.3;8.2.3 Complex Structures MO Diagrams by TSH Theory;735
14.4;8.3 Special Bonding in Adjacencies by Topological Isomers;738
14.5;8.4 Conclusions;746
14.6;References;746
15;9 Add on. The Bondon: A New Theory of Electron Effective Coupling and Density Ensembles;749
15.1;Abstract;749
15.2;9.1 The Need for Bondonic Theory in Quantum Chemistry;750
15.3;9.2 The Analytical Roots of Bondonic Theory;752
15.4;9.3 The Gravitational Side of Bondonic Theory;761
15.5;9.4 Modeling Graphene Systems by Bondonic Theory;776
15.6;9.5 Bondons on Graphene by Symmetry Breaking Modeling;790
15.6.1;9.5.1 Symmetry Breaking Phenomenology in Quantum Nanochemistry;790
15.6.2;9.5.2 Bondons by Symmetry Breaking;793
15.6.3;9.5.3 Goldstone Bondons on Graphene with Topological Defects;798
15.7;9.6 Conclusions;802
15.8;References;803
16;Appendix: Atomic Two-Electron Integrals;807
17;Index;822