Quantum Nanochemistry, Volume Three : Quantum Molecules and Reactivity

567 Pages·2016·30.579 MB·English

by  Putz, Mihai V

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90000
ISBN: 978-1-77188-135-79 0000 Volume 3
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QuantuQmua Nnatunmoc hNeamnoiscthrye:m 5i-sVtroylu: m5-eV oSleutm: e Set:
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Quantum Nanochemistry: 5-Volume Set:
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QUANTUM
NANOCHEMISTRY
(A Five-Volume Set)
Volume III:
Quantum Molecules and Reactivity
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
QUANTUM
NANOCHEMISTRY
(A Five-Volume Set)
Volume III:
Quantum Molecules and Reactivity
Mihai V. Putz
Assoc. Prof. Dr. Dr.-Habil. Acad. Math. Chem.
West University of Timişoara,
Laboratory of Structural and Computational Physical-Chemistry
for Nanosciences and QSAR, Department of Biology-Chemistry,
Faculty of Chemistry, Biology, Geography,
Str. Pestalozzi, No. 16, RO-300115, Timişoara, ROMANIA
Tel: [phone]; Fax: [phone]
&
Principal Investigator of First Rank, PI1/CS1
Institute of Research-Development for Electrochemistry
and Condensed Matter (INCEMC) Timisoara,
Str. Aurel Paunescu Podeanu No. 144,
RO-300569 Timişoara, ROMANIA
Tel: [phone]; Fax: [phone]
E-mail: [email protected]
URL: www.mvputz.iqstorm.ro
CRC Press Apple Academic Press, Inc
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When you’re a quantum chemist, it’s like you’re sitting at the top
of the mountain. The distinction between biochemistry, inorganic,
and organic chemistry are less important, as all of chemistry
revolves around what the electrons are doing in molecules,
and that domain can be best “seen” by applying theory.
(Rodney J. Bartlett, 2007)
To XXI Scholars
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
CONTENTS
List of Abbreviations .................................................................................xiii
Preface to Five-Volume Set .........................................................................xv
About the Author .......................................................................................xxi
Foreword to Volume III: Quantum Molecule and Reactivity ..................xxiii
Preface to Volume III: Quantum Molecule and Reactivity .....................xxvii
Chapter 1. Modern Quantum Nature of the Chemical Bond:
Valence, Orbitals and Bondons .................................................................1
Abstract .......................................................................................................2
1.1 Introduction ........................................................................................3
1.2 Valence Bond Theory .........................................................................5
1.2.1 Adiabatic Approximation .......................................................5
1.2.2 The Virial Theorem on the Molecular Systems .....................9
1.2.3 The Chemical Bond Through the Valence Bond
Method (VBM) ....................................................................12
1.3 Molecular Orbital Theory of Bonding ..............................................22
1.4 Sub-Quantum Chemistry: Chemical Bonding
Field and Bondons ..................................................................34
1.4.1 Introducing Chemical Field .................................................35
1.4.2 Predicting the Bondonic’s Existence ...................................38
1.4.3 Chemical Bonding by Bondons ...........................................45
1.4.4 Chemical Bonding as a Bosonic Quantum Condensate ......55
1.4.4.1 ψ-Theory of Bose-Einstein Condensation ............55
1.4.4.2 DFT adapted to Bose-Einstein Condensation .......58
1.4.4.3 Local Density Approximation of
Bose-Einstein Condensation .................................61
1.4.4.4 Heitler-London Bondonic Condensation ..............64
1.4.4.5 Molecular Orbitals’ Bondonic Condensation .......70
1.5 Conclusion ........................................................................................82
Keywords ..................................................................................................84
References .................................................................................................85
viii Contents
Author’s Main References ...............................................................85
Specific References .........................................................................85
Chapter 2. Molecular Structure by Quantum Chemistry .............................93
Abstract .....................................................................................................94
2.1 Introduction ......................................................................................94
2.2 Inter-Atomic Vibration, Interaction, and Bonding Localization ......97
2.2.1 Harmonic Oscillator in Biatomic (H2) Molecule ................97
2.2.2 Van Der Waals Biatomic (He-He) Interaction .....................99
2.2.3 Orbital vs. Density Electronic Localization in Bonding ....103
2.3 Molecular Structure by Symmetry Analysis ..................................111
2.3.1 Molecular Symmetry Groups ............................................111
2.3.1.1 Symmetry Elements and Operations ..................111
2.3.1.2 Building the Symmetry Groups ..........................125
2.3.2 Symmetry Adapted Linear Combinations
(SALC) Wave Functions ....................................................142
2.3.3 Linear Combinations of Atomic Orbitals
(LCAO): Hückel Approximation .......................................153
2.4 Atoms-in-Molecule Coordination by Crystaline
Fields’ Analysis ...............................................................................159
2.4.1 The Separation Origin of the Four-Lobed Orbitals............159
2.4.2 The Quantum Model of the Crystal Field ..........................170
2.4.3 Multi-Electronic Orbitals in the Crystal Field ...................180
2.5 Molecular Coordinative Complexes by Ligand
Fields’ Analysis ..............................................................................196
2.6 VSEPR Model of Chemical Bond ..................................................205
2.7 Conclusion ......................................................................................215
Keywords ................................................................................................217
References ...............................................................................................217
Author’s Main References .............................................................217
Specific References .......................................................................218
Chapter 3. Quantum Chemical Reactivity of Atoms-in-Molecules ............225
Abstract ...................................................................................................227
3.1 Introduction ....................................................................................228
3.2 Coexistence of Atoms-in-Molecules ..............................................230
3.2.1 Density Description of AIM ..............................................230
3.2.2 Energy Description of AIM ...............................................232
3.2.3 Population Analysis of AIM ..............................................239
Contents ix
3.3 Electronegativity of Atoms-in-Molecules ......................................242
3.3.1 Electronegativity as Connectivity of
Atoms in Molecules ..........................................................242
3.3.2 Fractional Charge Electronegativity ..................................245
3.3.3 Density Functional Electronegativity ................................249
3.3.4 From Chemical Potential to Electronegativity
Relationships .....................................................................252
3.3.5 Electronegativity Additive Equalization Principle ............262
3.3.6 Observable Electronegativity by Averaging of
Atoms in Molecules ...........................................................267
3.3.7 Modeling Electronic (De)Localization in
Chemical Bonding .............................................................272
3.3.8 Electronegativity Geometric Equalization Principle .........274
3.3.9 Connecting Absolute and Mulliken
Electronegativities by Reactivity .......................................277
3.3.10 Poly-Atomic Electronegativity by Chemical Hardness
and Fukui Function ............................................................279
3.4 Chemical Hardness of Atoms in Molecules ...................................282
3.4.1 Iterative Chemical Hardness of AIM .................................282
3.4.2 Softness and Fukui Indices relating
Chemical Hardness ............................................................289
3.4.3 Sensitivity of Atoms-in-Molecules ....................................293
3.4.4 Note on Chemical Hardness Coefficients ..........................299
3.4.5 HSAB Principle and Maximum Hardness Index ...............302
3.4.6 Maximum Hardness Index of Lewis Acids and Bases ......307
3.4.7 Application Limits of HSAB Principle ..............................318
3.5 Chemical Reactivity by Frontier Fukui Index Principles ...............326
3.5.1 Chemical Hardness Principles Reloaded ...........................326
3.5.2 Frontier Controlled Chemical Reactivity ...........................330
3.5.3 Spin Effects on Chemical Reactivity .................................336
3.6 Molecular DFT Parabolic Dependency E=E(N) on
Reactivity Indices ...........................................................................343
3.6.1 Bivariate Electronegativity-Chemical
Hardness Relationship .......................................................344
3.6.1.1 Physical Necessity for Parabolic
E(N) Dependency ...............................................344
3.6.1.2 Chemical Realization for Parabolic
E(N) Dependency ...............................................345