Table of Contents
Preface V
List of contributing authors XIII
1 Synthesis meets theory: Past, present and future of rational chemistry Mauro Fianchini 1
1.1 Introduction 1
1.2 The past: Birth of a discipline 3
1.3 The present: Rise of a rational discipline 9
1.3.1 Electronic structure 11
1.3.2 Solvation schemes 17
1.3.3 Ensemble properties 18
1.3.4 Transition state theory 25
1.3.5 Kinetic models 30
1.3.6 Multi-scale models 31
1.3.7 Wavefunction analysis 33
1.3.8 Chemoinformatics and machine-learning 35
1.4 The future: Conclusions and author's perspectives 37
References 38
2 Close contacts at the interface: Experimental-computational synergies for solving complexity problems Juan Torras David Zanuy Oscar Bertran Carlos Alemán Jordi Puiggalí Pau Turón Guillem Revilla-López 53
2.1 Elucidation of the aluminum corrosion protection mechanism of silanes 55
2.2 Computational insights of the mica-supported deposition of dendrimers 58
2.3 An atomistic-scale portrayal of polyethylene film growth 63
2.3.1 Deposition of polymer chains on the metal substrate 64
2.3.2 Growth algorithm 65
2.3.3 Energy relaxation: Molecular dynamics 67
2.3.4 Force field details 68
2.3.5 Molecular dynamics: simulation details 68
2.4 A complementary computational-experimental investigations of DNA-hydroapatite biominerals 69
References 74
3 The halogen bond: Nature and applications Paulo J. Costa 81
3.1 Introduction 81
3.2 On the nature of the halogen bond: A longstanding debate 84
3.2.1 Latest theoretical insights 86
3.2.2 Surrounding environment effects on the nature and strength of halogen bonds 90
3.3 Method benchmarks 93
3.4 Applications 96
References 102
4 Effect of protonation, composition and isomerism on the redox properties and electron (de)localization of classical polyoxometalates Xavier López 107
4.1 Introduction 107
4.2 Background 109
4.2.1 Electrochemistry 109
4.2.2 Density functional theory 109
4.3 Influence of the heteroatom size on the redox properties of Keggin anions 110
4.4 pH-dependent electrochemical behaviour of α1/α2-[Fe(H2O)P2W17O61]7- isomers 117
4.5 Effect of electron (de)localisation and pairing in the redox properties of Wells-Dawson molybdotungstophosphates 121
4.5.1 Calculations on α-P2W18, α2-P2W17, α2-P2Mo3W15 and P2Mo6W1212 124
4.5.2 Calculations on α1- and α2-P2W1717Mo 125
4.6 Summary 130
References 130
5 Modeling of Azobenzene-Based Compounds V. Marturano V. Ambrogi N. A. G. Bandeira B. Tylkowski M. Giamberini P. Cerruti 135
5.1 Introduction 135
5.2 Modeling the trans-cis isomerization of azobenzene and its functionalized derivatives 137
5.3 Modeling molecules with the azobenzene unit in their constitutive structure 141
5.4 Achieving photo-controllable materials 144
5.4.1 Biomolecules 144
5.4.2 Molecular machines 146
5.5 Conclusions 147
References 147
6 Gas-phase high-resolution molecular spectroscopy for LAV molecules Iwona Gulaczyk 153
6.1 Introduction 153
6.2 Methylamine molecule 155
6.3 Measurements of spectra 157
6.4 Assignments and analysis of rovibrational spectra with Loomis-Wood for Windows program 158
6.5 Theoretical model 162
6.6 Assignment and analysis of the wagging state, v9 166
6.7 Assignment and analysis of the C-N stretching band of methylamine, v8 169
6.8 Assignment and analysis of the first excited torsional state, v15 172
6.9 Assignment and analysis of the asymmetric CH-stretching state, v11 174
6.10 Summary 174
References 175
7 Computer analysis of potentiometric data of complexes formation in the solution Renata Jastrzab Malgorzata T. Kaczmarek Bartosz Tylkowski Akira Odani 177
7.1 Introduction 177
7.2 Computer programs applied to stability constants calculations 179
7.3 General basis of computer methods 181
7.4 Factors affecting convergence process 182
7.5 Model verification 182
7.5.1 The convergence criterion 183
7.5.2 Comparison of standard deviations 183
7.5.3 Comparison of titration curves 184
7.5.4 Hamilton test (R) 185
7.5.5 Chi square test (x2) 185
7.5.6 Comparison of results from different computer programs 186
7.6 Examples of the use of calculated stability constants 186
Disclosure statement 191
References 191
8 Reactive extraction at liquid-liquid systems Karolina Wieszczycka 195
8.1 Reactive liquid extraction 195
8.1.1 Introduction 195
8.1.2 Classical solvent extraction 196
8.2 Reactive extraction 200
8.3 Extraction equilibria and stoichiometry of extracted metal complex 205
8.3.1 Chelating extractant 205
8.3.2 Modified Bromley's methodology 207
8.3.3 Pitzer model 207
8.3.4 Acidic organophosphorus extractant 212
8.3.5 Procedure of analysis 212
8.3.6 Extraction with hydrophobic extractant containing pyridinium cation 214
8.4 Kinetic of extraction 217
8.4.1 Example of kinetic study 218
8.5 Extraction at liquid-solid system 221
References 227
9 Membrane processes Katarzyna Staszak 231
9.1 Basic principle of membrane process 231
9.1.1 Retention 232
9.1.2 Membrane fouling 241
9.2 Membrane characterization 248
9.2.1 Introduction 248
9.2.2 Experimental characterization of membranes 251
9.2.3 Calculation method of membrane characterization 253
References 255
10 The problem of fouling in submerged membrane bioreactors - Model validation and experimental evidence Irene Tsibranska Serafim Vlaev Bartosz Tylkowski 261
10.1 Introduction 261
10.2 Membrane fouling modeling and validation 264
10.2.1 Fouling modeling 265
10.2.2 Larger-scale applications 267
10.2.3 Validation experience 269
10.3 Conclusions 275
References 277
11 Applicability of DFT model in reactive distillation Maciej Staszak 283
11.1 Introduction 283
11.2 Distillation process 284
11.2.1 Equilibrium approach 286
11.2.2 Nonequilibrium approach 288
11.2.3 Vapor-liquid equilibrium 290
11.3 Short outline of quantum modeling by DFT 291
11.3.1 Density functional theory 291
11.3.2 Basis sets 292
11.4 Quantum approach to VLE calculations 293
11.4.1 Continuum solvation models 293
11.5 Quantum approach to chemical reaction kinetics description 300
11.5.1 Intrinsic reaction coordinate 300
11.6 Summary 303
References 304
Index 309
