Bond analysis of metal element interactions in molecules and solids applying embedding and density functional techniques [Elektronische Ressource] / vorgelegt von Kathrin Claudia Götz

Kathrin Bartelheim

Informations

• Publié par: julius-maximilians-universitat_wurzburg
• Publié le: 01 janvier 2009
• Nombre de lectures: 16
• Langue: English
• Poids de l'ouvrage: 7 Mo

Extrait

 
 
BOND ANALYSIS OF METAL–
ELEMENT INTERACTIONS IN
MOLECULES AND SOLIDS APPLYING
EMBEDDING AND DENSITY
FUUNNCCTTIIOONNAALL TEECCHHNNIIQQUUEESS F T
 
Dissertation

Zur Erlangung des naturwissenschaftlichen Doktorgrades der Julius-Maximilians-
Universität Würzburg




Vorgelegt von
Kathrin Claudia Götz
aus Würzburg, Deutschland

Würzburg, 2009
 
  
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 








Eingereicht am: ___________________________________
An der Fakultät für Chemie und Pharmazie


1.Gutachter: ___________________________________
2.Gutachter:
der Dissertation

1.Prüfer: ___________________________________
2.Prüfer: ___________________________________
3.Prüfer: ___________________________________
des Öffentlichen Promotionskolloquiums

Tag des Öffentlichen Promotionskolloquiums: _____________
Doktorurkunde ausgehändigt am: ________________________





































Nicht müde werden
sondern dem Wunder
leise
wie einem Vogel
die Hand hinhalten.

Hilde Domin
(deutsche Lyrikerin, 1909-2006)



Contents
Part I – Introduction and Theoretical Background …..……1
1 Introduction …………………………………………………………………… 3
2 Foundations of Density Functional Theory ……………………………………7
2.1 Fundamentals: the Schrödinger Equation and the Hartree-Fock
Approximation …………………………….......……………………..8
2.2 From Hohenberg-Kohn theorems to the Kohn-Sham approach ….….11
2.2.1 The Hohenberg-Kohn Theorems ……………………………………11
2.2.2 The Kohn-Sham Approach .................................................................12
2.3 Functionals and Electron Holes – on LDA, GGA and Hybrids .........14
2.3.1 Density Matrices and Electron Holes ………………………………14
2.3.2 Modern Functionals ............................................................................17
2.4 Shortcomings of the DFT Approach .................................................20
3 Introduction to Density-Based Topological Tools …………………………...23
3.1 The Quantum Theory of Atoms in Molecules ....................................24
3.1.1 Basic Formalism .................................................................................24
3.1.2 Shortcomings, Criticism and Developments ......................................27
3.2 Real Space Functions for the Description of Electron Localization ...29
3.2.1 The Electron Localization Function ...................................................29
3.2.2 The Electron Localizability Indicator ................................................32
3.2.3 Comparison and Criticism ..................................................................34
Part II – Chemical Bonding in Transition Metal
Compounds ………………………………………………….37
4 Introduction ………………………………………………………………….39
I

5 Bonding Patterns in Dinuclear Iron Complexes – an Overview of
Metal–Metal Interactions …………………………………………………….43
5.1 Computational Details ........................................................................46
5.2 Bridged-to-Terminal Metamorphosis in Fe CO ...............................46 2 9
5.3 Metal–Metal Interactions in Supported Diiron Complexes ...............48
5.4 Conclusions ........................................................................................53
6 Extension of the Fischer/Schrock Concept …………………………………55
6.1 Computational Details .......................................................................57
6.2 Fischer and Schrock Carbenes ...........................................................57
6.3 Comparison between Singlet and Triplet Borylenes and Carbenes ...59
6.4 Exemplary Fischer- and Schrock-type Borylene Complexes ............60
6.5 Outlook ..............................................................................................63
7 Dependency of AIM and ELF Results for Bonding Analyses on Exchange
Correlation Functionals ....................................................................................65
7.1 Computational Details .......................................................................67
7.2 Optimized Structures ..........................................................................68
7.3 QTAIM Analysis ................................................................................69
7.4 ELF ......................................................................................78
7.5 Conclusions ........................................................................................81
8 Structure and Bonding in Supported Dinuclear Cobalt and Nickel Borylene
Complexes ……………………………………………………………………85
8.1 Compuational Details .........................................................................86
8.2 Experimental Background and Structure Determination ...................86
8.3 Bonding Analysis ...............................................................................89
8.5 Conclusions ........................................................................................94
Part III – Main Group Metals: Li–C Bonding and
Intermolecular Interactions in Methyl Lithium …………...95
9 Introduction ………………………………………………………………….97
II

9.1 Aggregation of LiR – Structure Forming Principles ..........................98
9.2 Prevalent Bonding Concepts in Organolithlium Compounds ..........100
10 Computational Methods .................................................................................103
10.1 Periodic Simulations .........................................................................104
10.1.1 Basic Formalism ...............................................................................104
10.1.2 Gaussian Basis Sets in Solid State Calculations ..............................108
10.2 Embedding Techniques ...................................................................109
10.2.1 Polarizable Continuum Models .......................................................110
10.2.2 Periodic Electrostatic Embedded Cluster Model ..............................111
11 Validation of Embedding Techniques for Modeling Environmental
Effects in Polar Organolithium Compounds ..................................................113
11.1 Computational Details .....................................................................116
11.1.1 Embedded Cluster Calculations .......................................................116
11.1.2 Solid State Calculations ....................................................................117
11.1.3 Functionals .......................................................................................117
11.1.4 Basis Sets ..........................................................................................117
11.1.5 QM Cluster Definitions ...................................................................118
11.1.6 Location of BCPs and AIM Basin Integration .................................119
11.2 Modeling Solid State Effects in MeLi .............................................121
11.3 Conclusions ......................................................................................126
12 Understanding the Structure-Reactivity Relationship of Methyllithium
Base Adducts .................................................................................................127
12.1 Computational Details ......................................................................128
12.2 Structure Formation and Agostic Interactions .................................128
12.2.1 Experimental Background and X-Ray Structure Determination ......129
12.2.2 Optimized Structures ........................................................................130
12.2.3 Agostic Interactions .........................................................................133
12.3 Electronic Structure Analysis ...........................................................135
12.3.1 General Aspects of Li–C Bonding in MeLi Clusters and Adducts ...135
III

12.3.2 Polarity Changes upon Deaggregation and Lewis Base
Coordination ....................................................................................137
12.4 Conclusions ......................................................................................140
Part IV – Summary ..............................................................143
4.1 Summary ..........................................................................................145
4.2 Zusammenfassung ............................................................................153

References ..........................................................................