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Chapter 1 Integrating Computed Crystal Energy Landscapes in Crystal Form Discovery and Characterisation |
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1 | (31) |
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1 | (2) |
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1.2 Computational Methodology for Predicting Molecular Crystal Structures |
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3 | (8) |
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3 | (3) |
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1.2.2 Searching the Conformational Phase Space and Estimating the Total Crystal Lattice Energy |
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6 | (3) |
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1.2.3 Search Methods for Finding Hypothetical Crystal Structures |
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9 | (2) |
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1.3 Applications of Computed Crystal Energy Landscapes |
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11 | (10) |
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1.3.1 Polymorph Screening and Characterisation |
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11 | (3) |
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1.3.2 Multicomponent Crystal Form Discovery |
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14 | (4) |
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1.3.3 Structure Solution from Powder X-ray Diffraction Data |
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18 | (3) |
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1.4 CCDC Blind Tests: Assessing Progress in Crystal Structure Prediction Methods (1999--2016) |
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21 | (5) |
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26 | (6) |
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26 | (1) |
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26 | (6) |
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Chapter 2 High Pressure Crystallography: Elucidating the Role of Intermolecular Interactions in Crystals of Organic and Coordination Compounds |
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32 | (66) |
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32 | (3) |
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2.2 High-pressure Experiments |
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35 | (3) |
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2.3 Continuous Anisotropic Compression |
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38 | (6) |
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2.4 Polymorphic Transitions |
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44 | (12) |
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56 | (3) |
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2.6 Multi-component Crystals |
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59 | (5) |
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2.7 Pressure-induced Reactions and Effect of Pressure on Photo- and Thermo-chemical Transformations |
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64 | (4) |
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68 | (30) |
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69 | (1) |
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70 | (28) |
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Chapter 3 Intermolecular Interactions in In situ Cryocrystallized Compounds |
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98 | (32) |
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98 | (1) |
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3.2 Methodology, Equipment and Instrumentation |
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99 | (4) |
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3.2.1 OHCD (Optical Heating and Crystallization Device) |
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101 | (2) |
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3.2.2 Problems and Concerns During the OHCD Experiment |
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103 | (1) |
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3.3 Applications of In Cryocrystallization |
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103 | (22) |
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3.3.1 Investigation of Strong and Weak Hydrogen Bonds (HBs) in In situ Cryocrystallized Liquids |
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104 | (2) |
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3.3.2 In situ Cryocrystallization Study of Halogen Bonding |
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106 | (5) |
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3.3.3 Investigation of Other Weak Interactions in In situ Cryocrystallized Liquids |
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111 | (6) |
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3.3.4 Computational Analysis |
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117 | (3) |
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3.3.5 In situ Cryocrystallization Study in Fluorinated Benzoyl Chlorides |
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120 | (4) |
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3.3.6 In situ Cryocrystallization in Organometallic Liquids |
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124 | (1) |
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125 | (5) |
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126 | (1) |
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126 | (4) |
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Chapter 4 Experimental Electron Density Studies of Inorganic Solids |
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130 | (29) |
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130 | (1) |
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4.2 Methods for Electron Density Studies |
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131 | (4) |
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4.3 Electron Density Studies of Inorganic Crystals |
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135 | (7) |
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4.3.1 Experimental Strategies and Challenges |
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135 | (2) |
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4.3.2 Challenges Related to Aspherical Modelling of Electron Densities in Inorganic Solids |
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137 | (2) |
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4.3.3 Analysis of Electron Densities in Inorganic Solids |
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139 | (3) |
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4.4 Few Reported Case Studies |
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142 | (11) |
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4.4.1 Electron Densities in Elemental Boron Allotropes |
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142 | (3) |
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4.4.2 Electron Density in Pyrope (Mg3Al2Si3012) |
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145 | (2) |
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4.4.3 Electron Densities in Pyrite and Marcasite Polymorphs of FeS2 |
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147 | (3) |
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4.4.4 Electron Density in Caesium Uranyl Chloride (Cs2UO2Cl4) |
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150 | (3) |
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153 | (6) |
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155 | (1) |
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155 | (4) |
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Chapter 5 Experimental Charge Density Analysis in Organic Solids |
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159 | (30) |
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159 | (2) |
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5.2 Experimental Requirements |
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161 | (2) |
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5.2.1 Good Quality Single Crystals and High-resolution X-Ray Data |
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161 | (1) |
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5.2.2 Multipolar Modeling of CD Data |
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162 | (1) |
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5.3 Evaluation of ED Features from the Experimental CD Model |
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163 | (5) |
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5.3.1 Quantum Theory of Atoms in Molecules (QTAIM) |
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163 | (2) |
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5.3.2 Source Function (SF) Analysis |
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165 | (1) |
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5.3.3 Non-covalent Interactions (NCIs) Descriptor |
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165 | (2) |
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5.3.4 Lattice and Interaction Energies from the CD Model |
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167 | (1) |
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5.3.5 Molecular Electrostatic Potentials |
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168 | (1) |
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168 | (15) |
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5.4.1 Evaluation of Intra- and Intermolecular Interactions |
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168 | (3) |
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5.4.2 Chemical Reactivity in Organic Solids |
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171 | (2) |
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5.4.3 Polymorphs and Cocrystals |
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173 | (3) |
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5.4.4 Halogen Bonding (XB) and Other a-Hole Bonding |
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176 | (2) |
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5.4.5 Validating the Concept of Charge Shift Bonding (CSB) |
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178 | (1) |
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5.4.6 Phase Transitions in Organic Solids |
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179 | (1) |
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5.4.7 CD Studies Under High Pressure |
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180 | (1) |
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181 | (2) |
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183 | (6) |
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183 | (1) |
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183 | (6) |
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Chapter 6 Charge Density Studies and Topological Analysis of Hydrogen Bonds in Proteins |
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189 | (22) |
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189 | (4) |
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6.2 Protein Charge Density Analysis |
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193 | (3) |
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193 | (1) |
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193 | (1) |
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6.2.3 Methodologies and Tools |
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194 | (1) |
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6.2.4 Multipolar Refinement |
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195 | (1) |
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6.3 Six Selected ECDA Studies |
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196 | (3) |
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6.4 Use of Neutron Diffraction Data |
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199 | (1) |
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6.5 Topological Analysis of Hydrogen Bonding |
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200 | (5) |
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6.5.1 Computation of Electrostatic Interaction and Dissociation Energies |
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200 | (1) |
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6.5.2 The Case of Human Aldose Reductase (hAR) |
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201 | (4) |
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205 | (6) |
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207 | (1) |
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207 | (4) |
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Chapter 7 Towards a Generalized Database of Atomic Polarizabilities |
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211 | (32) |
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Leonardo H. R. Dos Santos |
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211 | (4) |
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7.2 Theoretical Background |
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215 | (5) |
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7.2.1 Earlier Atomic Polarizability Databases and the Need for a New One |
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215 | (3) |
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7.2.2 Distributed Atomic Polarizabilities |
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218 | (2) |
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7.3 Constructing the Database |
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220 | (7) |
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7.3.1 Computational Details |
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220 | (1) |
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7.3.2 The Local Coordinate System |
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221 | (2) |
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7.3.3 Multivariate Data Analysis and Clustering |
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223 | (4) |
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7.3.4 Recognizing a Functional Group |
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227 | (1) |
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227 | (12) |
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7.4.1 Clustering the CH2 Polarizabilities |
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227 | (2) |
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7.4.2 Clustering all Functional Groups |
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229 | (1) |
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7.4.3 Using the Database to Compute Polarizabilities |
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229 | (10) |
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239 | (4) |
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240 | (1) |
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240 | (3) |
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Chapter 8 Solid-state NMR in the Study of Intermolecular Interactions |
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243 | (42) |
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243 | (1) |
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8.2 Essential Techniques and Parameters in Solid-state NMR |
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244 | (6) |
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8.2.1 Magic-angle Spinning, High-power Proton Decoupling and Cross Polarization |
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244 | (2) |
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246 | (2) |
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8.2.3 Dipolar Interaction |
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248 | (1) |
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8.2.4 Quadrupolar Interaction |
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249 | (1) |
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8.3 SSNMR and Hydrogen Bond |
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250 | (18) |
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8.3.1 Hydrogen Bond and Chemical Shift/Chemical Shift Anisotropy |
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251 | (8) |
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8.3.2 Hydrogen Bond and Dipolar Interaction |
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259 | (8) |
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8.3.3 Hydrogen Bond and Quadrupolar Interaction |
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267 | (1) |
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8.4 SSNMR and Halogen Bonds |
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268 | (7) |
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8.5 SSNMR and π--π Stacking |
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275 | (1) |
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8.6 Conclusion and Outlook |
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276 | (9) |
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277 | (8) |
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Chapter 9 Quantitative Analysis of Weak Non-covalent σ-Hole and π-Hole Interactions |
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285 | (49) |
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9.1 Introduction and Historical Perspective |
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285 | (3) |
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9.2 Nature of σ-Hole and Π-Hole Interactions |
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288 | (5) |
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9.2.1 σ-Hole Interactions |
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288 | (2) |
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9.2.2 π-Hole Interactions |
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290 | (3) |
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9.3 Hirshfeld Surface Technique |
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293 | (5) |
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9.3.1 Crystal Engineering and Models to Describe Crystal Packing |
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293 | (1) |
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9.3.2 Theoretical Background for Hirshfeld Surface Calculation |
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294 | (1) |
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9.3.3 Various Surfaces and Associated Fingerprint Plots |
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295 | (3) |
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9.4 Computational Methods |
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298 | (1) |
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9.5 Exploration of a-Hole Interactions |
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298 | (17) |
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9.5.1 Group VII Interactions (Halogen Bonding) |
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298 | (5) |
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9.5.2 Group VI Interactions (Chalcogen Bonding) |
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303 | (4) |
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9.5.3 Group V Interactions (Pnictogen Bonding) |
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307 | (4) |
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9.5.4 Group IV Interactions (Tetrel Bonding) |
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311 | (4) |
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9.6 Exploration of π-Hole Interactions |
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315 | (6) |
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9.6.1 Group III Interactions (Triel Bonding) |
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315 | (3) |
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9.6.2 Group V Interactions (Pnicogen Bonding) |
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318 | (3) |
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321 | (13) |
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322 | (1) |
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322 | (12) |
Subject Index |
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334 | |