Molecular Reaction Dynamics Raphael D
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Cambridge University Press 052184276X - Molecular Reaction Dynamics Raphael D. Levine Index More information Index 1, 1’ binaphtyl conformational twist 455 in the spectator limit 415 kinematic effects 402 1, 3 cyclohexadiene ring opening in real of reaction products in a polarization 402 time 386 chemiluminescent reaction 414 sense of rotation 411 analog computation 200 spherical basis vectors 408 + Ar +H2 stripping 23 angle of attack 14, 97 vector correlations 419, 422 collision-induced dissociation 23 angle of deflection 111 angular velocity 113 above-threshold ionization, ATI angle-dependent barrier to reaction 96, anisotropy parameter in 332 163 photodissociation 280 absorption, collision-induced 310 angle-dependent line-of-centers anti-Morse potential 198 abstraction reaction 14 model 97 Arrhenius activation energy 1, 75, accommodation to the surface 480 angle variable 198 79 action variable 198 angular distribution see also Tolman expression activated adsorption 482 classical divergence in the forward Arrhenius equation 1, 74 activation energy 1 direction 119 by saddle-point integration 101 definition 74 for surface scattering 479 historical background 25 in transition state theory 254 hard-sphere-like in the backward surface desorption 480 negative 196 direction 119 Arrhenius pre-exponential factor 1 Tolman expression 79, 103 in complex mode reactions 140 high/low 255 adiabatic limit 149, 268, 372 forward-backward symmetry 140 see also entropy of activation, steric adiabaticity parameter 372 in direct reactions 138 factor and momentum gap 374 in photodissociation 280 associative desorption 484 and response time 373 in photodissociation by linearly asymmetry parameter 422 for curve crossing 381, 382 polarized light 281 atmospheric detergent 283 radiationless transitions 392 in reactive collisions 8, 142, 237 atmospheric photochemistry 281 adsorbate-induced surface reconstruction of state-selected molecules 171 atomic flames 179 476 quenched by reactive scattering 143 atomic force microscope, AFM coverage dependence 493 rebound reactions 142 230 adsorption resonance scattering 145 ATP synthase motor 228 activated 482 spectator stripping 8 attractive potential 88 dissociative 90, 482 sprinkler model 139, 140, 422 attractive potential energy surface 155, Langmuir isotherm 495 angular momentum 49, 144 179 on stepped surfaces 486, 487 conservation 109 autocatalytic process 497 aligning molecules with polarized conservation of total angular radiation 398 momentum 402 Ba + HI kinematic constraint 403 with strong lasers 323 definition 110 opacity function from products’ alignment 396 degree of orientation and rotation 404 and orientation in surface scattering alignment 407 backwards scattering 120 412 disposal 405 bacteriorhodopsin 386 in terms of quadrupole moment in phase space theory 249 photoisomerization 387 409 inelastic collisions 412 ballistic collisions 389 543 © Cambridge University Press www.cambridge.org Cambridge University Press 052184276X - Molecular Reaction Dynamics Raphael D. Levine Index More information 544 Index barrier height 152, 206 Breit–Wigner phase shift 135 long-time dynamics 261 and barrier location profile 136 pattern formation 20, 492 Evans-Polanyi model 162, 195, 268, bright state 272 sensitivity to initial conditions 20 464 decay rate 275 charge neutralization 107, 378 Hammond postulate 162 revival 274 charge transfer 86, 385 systematics 155, 466 Brownian dynamics 175 adsorbate-surface 477 in a reaction series 465 brute force orientation 397, 424, 425 hardness 89 in a unified model 467 bumpy quasi-continuum 199 harpoon mechanism 86 vs approach angle 96 Butler-Volmer law 464 in solution 437 barrier-crossing rate oxidation-reduction 25 Grote-Hynes correction 456 C2H2 spectra at increasing partial 156 in the high friction limit 456 resolution 277 rate constant 438 unified model for barrier crossing in C2H5 +O2 combustion reaction 156 charge-directed action 227 solution 464, 472 Ca∗ + HCl electronic orbital control chemical activation 216 see transition state theory 399 chemical laser action 26, 359 benzene multiphoton ionization and cage effect 18, 19, 427, 442, 445, 459 chemiluminescence 6, 239 fragmentation 309 coherence 447 in four-center reactions 24 bimolecular spectroscopy 310 in clusters 445 chemistry in space 107, 282 binning trajectory results 199 mechanical blocking 445 chemistry is local 4 blackbody emission–molecular 274 capture model 92, 107 chirped pulse 328 bobsled effect 179, 192 cross-section 92 chirped pulses for stereodynamics bond breaking in real time 337 CARS spectroscopy 11 401 Born model for solvation 431 Cartesian contour maps 237 CHOCHO photodissociation 422 thermodynamic cycle 433 catalysis by enzymes 430 Cl+CD4 preferential DCl Born–Oppenheimer separation 148, 149 center of mass, definition 64 alignment 418 − breakdown 193, 267 center-of-mass coordinate system 63 Cl +CH3Br reaction 226 − conical intersections 329 central collisions 117 Cl +CH3Cl reaction, stereochemistry of curve crossing 378 centrifugal barrier 51, 53, 55 the transition state 188 gap 357; how large is a large barrier to reaction 91 Cl+CH4 peripheral reaction mechanism gap? 270 see capture model 416 in the transition state region 268 centrifugal energy 112 approach geometry 415 diabatic description of electronic states centrifugal force 55 reaction at different impact parameters 380 C H bond activation 4, 499 418 + exponential gap for non-adiabatic CH2=CH2 +CH2=CH2 complex mode Cl+H2O reaction coordinate 299 transitions 382 reaction 256 Cl + HI reaction 4, 168 radiationless transitions 272 CH2CO photodissociation and cone of acceptance 169 picket fence model 275 photoisomerization 294 surprisal analysis 258 bottleneck to reaction 212, 252 potentials for photodissociation and transition state spectroscopy 27 in solution 452 photoisomerization 294 classical action 198 Br + HCl reaction unimolecular dissociation 295 classical trajectories 11, 97, 170 isotopic enrichment 324 CH3 +CF3 reaction, surprisal analysis complex mode 186 laser pumped 324 256 direct reactions 172 Br + I2 reaction CH3Br photodissociation on LiF 490 for energy transfer collisions 391 from a restricted initial state 58 CH3NO2 multiphoton long times 261 in real time 341 dissociation/isomerization 306 Monte Carlo sampling 176 proceeding via the BrI2 intermediate potential for dissociation and need for averaging 173 58 isomerization 306 prompt 187 branching ratio 76 chaos 20 clocking bimolecular collisions 341 BrCH2COCl photodissociation deterministic 174, 199 clocking by collisions 217 270 erasure of details 195, 218 by fluorescence 217 © Cambridge University Press www.cambridge.org Cambridge University Press 052184276X - Molecular Reaction Dynamics Raphael D. Levine Index More information Index 545 clusters 445 complex mode reaction 169, 185, 216 transition state spectroscopy 12 1 cage effect in photodissociation 446 O( D)+D2 14 with ultrashort pulses 348 coulomb explosion 326, 332 sprinkler model 139, 140 cooling by supersonic expansion 289 dissociation of 223 computational chemistry 4, 26 cooperative behavior 260 size effects in cluster dynamics 473 forces 26 coordinate transformation in reactive van der Waals 58, 301, 375 gradient methods 156, 198 collision 405 CO oxidation on Pt 492 on the fly 159, 223 corresponding states 47 phase diagram 495 surface chemistry 26 corrosion reactions 486 role of surface reconstruction 494 computing on the fly 159, 198 coulomb explosion 326, 332 CO2 laser 368 concerted vs. sequential bond forming cross-section 31 coherence effects 354 344 see collision cross-section, differential decay of coherence 355 Condon approximation 328 cross-section, reaction for processes in solution and/or in cone of acceptance 95, 98, 163, 168, cross-section, large molecules 341 395 orientation-dependent HgI2 photodissociation Cl+HI169 cross-section Hg–I coherent vibration 340 opens up when the reactant bond is crossed molecular beam scattering 12, in reaction products 340 stretched 189 230, 236 see also interference Rb+CH3I reaction 27 cumulative reaction rate 208 coherent control 29, 320 configuration integral, as a potential for curve crossing 378, 380 by interference 321 mean force 454 curve crossing model 87, 89 by two-photon ultrafast excitation configuration of no return 202 dissociative adsorption 483 350 conical intersection 150, 196, 197, 259, excimer lasers 88 coherent rotational motion 353 268, 329 for dissociative chemisorption 90 coherent state 198, 336 in the H3 potential 160 reactive collisions 162 coherent vibrational motion 18, 340, in the LEP(S) potential 161 harpoon mechanism 86, 87; 349 in the ring opening of cyclohexadiene experimental data 103 coincidence measurements 423 388 strong laser field 99 collision cross-section 31, 34 motion towards 346 cyclobutene ring opening 344 as sum over partial waves 133 connectivity diagram 197 cyclobutene ultrafast isomerization 344 conservation 85 conservation of angular momentum 109, cyclopentanone ultrafast divergence in classical mechanics 57 110 dissociation 345 for hard spheres 39, 57, 69 conservation of total angular momentum microscopic definition 56 110, 402 D+I2 flux-velocity contour map 234 velocity dependence 46, 70, 124 constrained geometries 59 bent transition state 236 collision frequency 37 control 3 D2 + OH reaction 12 collision in the c.m. system 112 by interference 321 dark state 275 collision number, Zr 358 by pump and probe 350 tiers 276 collision rate constant 68 by strong laser field 25, 322 decay into a quasi-continuum 274 collisional ionization 379 by