Molecular body vs. molecular skeleton Ideal surface 1, 29

Transcription

1 Subject Index Acid catalysis 244, 245, 247, 249, 252 Bonds-pairs 177, 178, 184, 185, 190, 191, Activation 207, Activation barrier 160, 233, 242, 249 Bottleneck 291, 299, 307, , 336, Activation energy 233, 246, 247, 306, 357, 359, , 312, 314, 331, Butane 5, 14, Adiabatic potential, vibrational-rotational CASMCSCF 148, , , , 325, 338 CASSCF 150 Adiabatic states, electronic 312 Adiabatic states, vibrational 312, 314, 322 Adiabatic surface 147, 279 Allowed and forbidden pathways 205, 206 Allowed reactions 110 Allyl 180, 183 AM1381 Analytic expansion 8, 10 Analytic gradient 33-35, 45, 49, 348, 349 Anchor state 202, 203 Angular momentum 349, 352, 353 Concerted 151 Catalysis 231, 242, 244, 245, 249, 251 Catchment regions 59-61, Cation-anion recombinations 208 Cavity 223, 380 CHj transfer 197 Charge exchange 261 Charge transfer 114, 130, , 158, 160, 200, 203, 232, 235, 237, 240, 249, 251, 276, 277, 279 Chemical reactivity 147 Clausius-Mossoti equation 380 Collision integrals 281 Antibonding 166, 174, 176, 177, 182, Concerted transition structure 156, 245, 188, Asymptotic expansion 271 Asynchronous 151, 204 Atom abstractions 193 Avoided crossing 193, 194, , 200, , 210, 279 Configuration interaction 190, 198, 207 Conformational rearrangements 340, 374 Continuum 223, 231, , 244, 379 Contour surfaces 77, 79, 80, 81, 83, 84, 89, 91, 93, 96, 325, Barrier 165, 166, 193, 196 Coriolis coupling 352, 356 Betti numbers 13-15, 17, 18, 28 Correlation 194, 201 Bifunctional catalysis 231, 242, , Coulomb parameters , 252 Counting 295 Binomial coefficients 13, 17 Coupling functions 351, 352, 357 Biradical intermediate 204, 206 Covalent bond 166, 173, 177, 202 Bond distortions 207, 208 Covalent curves 196, Bond-diagram 167, 177, 178, 184, 190, Covalent determinants 173, 177, Critical point relations

2 388 Critical points 33-35, 48-49, 311 Crossing point 199, 205, 207, 208 Cumulative reaction probability 358, 359 Curvature coupling 319, 322, 352, 353, 355, 362, 363 Electrostatic interaction energy 219 Elimination reaction 203 Energy first derivatives 33-35, 45, 49 Energy second derivatives 34, 45, 57, Curvature of reaction path 304, , Energy third derivatives , 335, 339, 352 Entropic effects 232, 245, 292, 307, 325, Curvature properties 77, , Curve crossing diagrams 165, 166 Enumeration of internal coordinates 39- Cycloaddition 102, 131, 149, 152, 156, , 244, 378 Ethane 11, 14, 15 Cyclobutane 205 Ethylene hydrogenation Cyclopropenyl 180, 182 Exchange integral 106, 117, 155 Deflection function 264, 265, 266 Exchange parameters 149 Deformation energy Exchange reaction 202 Density of states , 358 Excited state 177, 196, 199, 201, 207, Determinant-mixing 171, 174, 177, Diabatic surface 101, 102, 117, 125, 127, Feynman path integral 365, , 133, , , 150, 160- Flux , FO-VB diagrams 184, 185, 190, 202 Diels Alder Reaction 147, 158, 206, 378 Forbidden reaction 152 Differential cross section , 263, Force constant 5, 6, 8, , 274, 282 Force constant matrix 34, 45, 47, 49-50, Diffusion coefficients , 350, 351, 364 Discrete 231, 233, 235, 379 Free energy of activation 232, 245, 306, Dispersion energy ,312,313,331, Displacement reactions 197 Friction 308, 333, 334, 365 Dividing surface 304 Friedel-Crafts reaction Dummy atoms Gaussian 86, 33, 36-37, Dynamic shape properties 93 Generalized Langevin equation 232, 333, Effective Hamiltonian Electric field 231, 244, Generalized transition state 299, 381 Electric permittivity 221 GEOMO 380 Electron transfer 176, 203, Global analysis of PES 56-58, 63 Electrophile 203 Gradient 5, 6, 8-10, 33-35, 45, 49, 376 Electrophilic substitution 226, 247, 251 Gradient length 7

3 H-atom transfer , , 334, Maxima 5-9, 11, 13-18, 20, 23, 24, , 338, 339, 348, 353, 354, 368 MCSCF 110, 112, 116, 120, 126, 140, Heisenberg Hamiltonian 101, , 143, 152, 154, , 131, 133, 136, 140, 143, 147, 149, Menschutkin reaction , 158, 160, 169, 180 Minima 2, 5-11, 13-18, 20, 22, 24, 26, Heitler-London 174, , 182, 183, 28, 33-35, , , Minimum energy path 48, 49, 51, 304, Hessian 34,45,47,49-50,376, , , , , 331, HOMO 226, ,348,349,353,355,357,368, 382 HOMO-LUMO Mixed-valence species 185 Homology groups 83 MNDO 380 Homotopy group Mobius 182, 185, 186 Huckel 181, 185 Molecular beams 263, 269 Hydrocarbons 17, Molecular body vs. molecular skeleton Ideal surface 1, 29 78,79 Image state Molecular Dynamics 231, 240, 380 Index of critical point 5-12, 14-20, 27, Monte Carlo 231,233,234,237,238, Induction energy 219 Internal coordinates 36-45, Intersection curves 194 Ionic exchange 197 Jahn-Teller mechanism 184, 190 Kekule structures 182, 183, Ketoenolic tautomerism Kinetic measurements 210 Knots and chirality polynomials 84, 85 Lewis structures 167, 178 Linear free energy relations Linear reaction path 348, 353, 357, 364, 368 Long bond 167, 189, 198 LUMO 226, 378 Marcus theory 208 Matrix elements 167,171,172,176,180, , 200, Multiconfiguration TDSCF 367 Multipoles 220, 225 Newton-Raphson optimization step Nodal properties 205 Non-ideal surface 1, 29 Non-linear Schrodinger equation 367 Nonbonded interactions 207 Normal coordinates 311, 314, 330, 350, 353, 356, 357 Normal mode 162 Nucleophile 203 Nucleophilic substitution 208, 226 Optimization 33-51, Orbital interactions 210 Orbital symmetry 206 Oriented relative convexity 82 Overlap repulsion 170, 171, 186, 189 Parallel algorithm for quasi global optimization 55,

4 390 Partition functions 293, , 309- Recrossing 232, 240, 241, 298, 299, 323, 312, 331, , 333 Pericyclic reaction 206 Reference cluster approach Permutations Regiochemical pathways 204 Perturbation language 177, 196 Relative convexity 82 Phase space , 307, 308, 332 Relaxation times 222, 235, 308, Polarizability 220 Resonance 170, 177, 183, 192, 207, 208 Polyrate 381 Rotation-inversion 4 Potential Energy Surfaces 34, 193, 231, Rotational excitation 261, 275, , 250, 291, 292, 294, , 347, Rumer functions , 354, 355, 368, 374 Rumer spin functions 162 Propane 14-16, 20 Saddle point 2, 5, 7-10, 13, 15-18, 20, QMRE 207, , 26,33-35, 45-46,48-49, 304,305, Quadratic expansion 5, 8, 35-36, , 324, 326, 329 Quasi-Newton methods for optimization Radical anion 200 Radical attacks 293, , 335, 338, 339 Radical reactions 193, Reaction barriers 148 Reaction coordinate 160, 197, 201, 233, 235, 236, 241, 244, 247, 249, 251, 252, 292, , , , 352, 360, 361, 364, 365 Saddle point optimization SCD 165, 194, , , SCF 226 Second derivative 5, 7, 8 Semiclassical approximation 264, 266, , , 360, Shape groups 77, 80, 81, 83, 84 Singlet-pairing 174, 175, 177, 181 SN2 reaction 35,192,197,208,209, , 240, 241, , 380 Reaction Field 225, 231, 252 Solute-solvent interactions 221 Reaction mechanism 55-56, 59, Solvation 221, 231 Reaction path 48-51, , 307, 311, Solvation free energy , , 335, 337 Solvation parameter Reaction path Hamiltonian 292, 297, 300, Solvent , 351, 352, 355, 360, 362, 364, 368 Solvent dynamic effect 231, 240, 331- Reaction profile 162, 232, 233, 249, 250, 334, , , , 331, 350 Solvent effects 231, 232, 241, 379, 293, Reactive flux , 312, 319, , Reactivity patterns 165, 193 Solvent fluctuations 237, 238, 241

5 Solvent reorganization 232, 233, 237, Transition state 33-35,45-46,48-49, 108, 238, , 129, 142, , 158, 162, 192, Solvent static effect 231, 232, 235, 331, 196, 197, 199, 200, , , , , 331, 332, , Space-orbitals , 349, 353, 355, 361, 376 Spin correspondence 214 Transition state optimization Spin transfer 192, 193, 197, 202, 203 Transition state theory 222, 232, 241, Spin-eigenfunction 167, ,298, , 381 Spin-orbital , 175, 195, , Translation Transmission coefficient 240, 241, 309, Spin-pairing 174, 177, 178, 181, 193, 313,317,323,335, , 201, 203, 205 Triionic structures 198 Stationary points 33-35,48-49,234,249 Triplet state 173,174,177,180, , Statistical approximations 294, 306, 308, 190, 194, 196, 205, , 333, 356, 360 Tunneling 291, 292, 308, 309, , Stereochemistry I, 5, 14, , , 355, 362, 363, 382 Strong coupling of internal coordinates Valence Bond 102, 111, 112, , , 121, 125, 133, , 143, 144 Substituent effects , 179, 191, 193, 194, 196, 197, Supra-antara 204, , 203, , 213 Supra-supra 204, 205 Van Vleck method 379 Symmetry 245, 247, 376, 303, 311, 325 Variational transition state theory 292, Symmetry and dummy atoms Symmetry and optimization VB determinants 165, , 178, 180, Symmetry and transition vectors 3 185, 211, 215 Symmetry constraints on PES 70, 72 VB-mixing diagram 173, 176, 179, 181- Synchronous , , 195, 199 Synthesis design on PES 54, 57, 63 VBCM 165 TDSCF 366 Vertical excitations energies Testing stationary points Yamanouchi-Kotani , 126 Thermal conductivity 280 Z-matrix 36-44, 46-47, 376 Thermal diffusion 280 Zwitterionic determinants 173, 175, 177- Topological periodicity 11, 13, 14, , Topology 1.. 5, 10, 11, 13-20, Total cross section 261, 274 Torus