563

Subject Index

ab initio calculations, 45, 52, 58, 109, 112, 231, 235, 237, 291-2 absorption spectra, 505, 520, 543 absorption spectroscopy, 542 ac electrode discharge, 5 acetylene, 283, 421 activation energy, 279 adiabatic ionization energy, 102, 107, 133 adiabatic ionization potential, 2, 20, 26 ammonia dimer cation,

dissociation energies, 146 equilibrium structure, 158-9 potential energy curves, 144

ammonia dimer, 102, 108, 112, 122 ionization energies, 147-9 ionization, 138 potential energy curve, 141

ammonium cation, 102 appearance energy, 145

angular distribution parameter, 384-5 angular momentum transfer, 387 aniline, 274 anisotropy factor, 509 appearance energy, 102, 188 appearance potential, 24 area detectors, 394-5 symmetry parameter, 384 Auger effect, 315 Auger process, 301 Auger spectrum, 316 auto-proton-transfer, 102, 163 autoionization resonance, 351,496 autoionization, 2, 11, 16, 36, 37, 219, 264, 267, 474

in vinyl radical, 24 autoionizing structure, 12

"backgammon" detector, 395 benzene ions, 274, 277 benzene, 274 benzyl ion, 280 beta-photoelectron asymmetry, 362 Beutler-Fano profiles, 183 bimolecular reactions, 496 1, 2-bis(p-toluenesulfonyl) ethane, 49-50 bond energies, 3, 9-10, 12-15, 18

of SnHn, 19 of ethane, 20 of ethylene, 20 role of hybridization, 19

Born-Oppenheimer approximation, 381, 418-20 boron hydrides,

PIMS of, 27 bond energies, 30 dimerization energy, 27, 29

branching ratio, rotationally resolved, 371

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breakdown diagram, 261-2 of isobutane, 272 of methane ion, 286

bromobenzene, 279, 281 bromotoluene ions, 275-6, 280

CFS method, 397 CIS method, 397 CIS scans, 368 CMSM calculations, 425 carbon dioxide, 51, 425 carbon monoxide, 410, 480

detection, 453 carboxylic acids, 111 chalcogen hydrides, PIMS of, 9 charge exchange, 276 charge separation mass spectrometry (CSMS), 299, 302 charge separation, mechanisms, 334-7 chemical abstraction reactions, 5 chemical reaction method, 7 chemical thermometers, 287 chlorobenzene ion, 277, 283 chlorobenzene, 274 chloroform, 49 circularly polarized VUV, 445—6 coincidence measurements, 2 coincidence statistics, 309 collection efficiency, 260 collection—detection efficiency, 311—2 collisional ionization, 303—4 constant ion state (CIS) spectrum, 359, 368-9 continuum channel coupling, 347, 363, 366, 369 continuum-continuum coupling, 401, 426 Cooper minimum, 380, 396 Cooper-Zare formula, 387 core electron excitation, 347, 366 core electrons, 360 core-hole resonance, 369 Coulomb explosion, 304, 336 Coulombic repulsion, 536 cyanogen, 422 cylindrical mirror analyzer, 391-2

dc electrode discharge, 5 deferred charge separation, 326 diborane, photoionization, 28 1, 2-dibromoethane, 50, 52 dichloro-, difluoromethane, 72 1, 2-dichloroethane, 50, 52, 54 differential cross section, 381-3 differential pulsed PEPICO scheme, 243 1, 2-difluoroethane, 48-54, 66-70

Hel photoelectron spectrum, 51-2 ionization energy, 52

1, 2-difluoroethyl radical, 45 PES, 67, 70

/?/?'-dihydroxyethyl ether, 50 dimer cations,

appearance energies, 156 dissociation energies, 160 hydrogen-bonded, 160 ionization energies, 154-6

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dipole approximation, 383-4 direct ionization, 267 dispersed fluorescence, 346-8, 361, 363, 519 dissociation energies, 188, 195, 215

of dimer cations, 147 of water dimer cation, 136

dissociation lifetimes, 223, 228, 238 dissociation limit, 276 dissociation rate, 274-5 dissociative attachment, 27 Doppler lineshape analysis, 455 double photoionization, 299 double resonance spectroscopy, 467 double resonance, 372

electrical discharge, 242 electron impact, 302 electron spectroscopy, 351 electron transmission function, 264 electronegativity, 9 electronic dipole matrix element, 356 1, 1-elimination of hydrogen, 202 1, 2-elimination of hydrogen, 202 entropy of activation, 279 equilibrium bond distance, 232-3 equilibrium bond length, 44 equilibrium density, of water dimer cation, 135 equilibrium geometries, of ammonia dimer, 140-2 equilibrium mass spectrometry, 216, 231 equilibrium structure,

of ammonia dimer cation, 140 of ammonia dimer, 140, 142-3

ethyl cation, classical ionic structure, 64 nonclassical ionic structure, 64

ethyl radical, structure, 26 excitation spectroscopy, 452-5 extreme ultraviolet radiation, 300

false coincidences, 269-70, 309, 322 Fano effect, 478 Fano line shape, 187 fast atom bombardment (FAB), 304 field ionization kinetics, 276 fluorescence cascades, 352 fluorescence cross section, 506 fluorescence polarization, 353 fluorescence spectroscopy, 352, 542 fluorescence spectrum, 349,359, 505, 523

rotationauy resolved, 370 fluorescence, 268-9 fluorine atom abstraction, 47 1-fluoro ethane, 48-50 fluoroethane, 62 1-fluoroethyl radical, 45, 62-6

PES, 61 2-fluoroethyl cation, 64-5, 69 2-fluoroethyl radical, 57, 64-6, 68-9 fluoroethyl radicals, 49 formic acid dimer, 113-4, 118-9 four-wave mixing, 439 fourfold coincidences, 327-9

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Franck-Condon approximation, 2, 351, 355-8 Franck-Condon breakdown, 360 Franck-Condon calculations, 44 Franck-Condon factors, 20, 24, 30, 163, 170, 272-3, 237, 349-50, 356, 488, 495 Franck-Condon gap, 267, 274 Franck-Condon principle, 10, 108, 140, 381, 385, 421 Franck-Condon process, 331 Franck-Condon profile, 219 Franck-Condon region, 144, 332 Franck-Condon transitions, 36, 232 free jet molecules, 506 free radicals, 2

by abstraction reactions, 7 microwave discharge and chemical reaction source, 8 photoionization studies, 3-4 pyrolysis source, 6 source, 3

geometrical structure, 2 geometries, 1, 2-difluoroethyl cation (X\A), 59

1, 2-difluoroethyl radical (X2A), 59 1-fluoroethyl cation (X*A), 55 1-fluoroethyl radical (X2A), 55 2-fluoroethyl radical (X2A), 56 ethyl fluorine cation (X\A), 56 of ammonia dimer, 123 of water dimer, 125

germanium (TV) hydride cation, structure, 23 germanium (IV) hydride,

PIMS, 23 germanium hydrides, 17

PIMS, 14 bond energies, 18

halobenzene ion, 281 hapooning mechanism, 547 Hartree-Fock level, 363 Hartree-Fock limit, 45 He(I) photoelectron spectra,

of ammonia, 122 of formic acid, 119 of methanol dimer, 121 of water dimer, 116, 134 of water vapor, 115

He (I) photoelectron spectrometer, 104 hemispherical analyzer, 263, 392-3 hemispherical electrostatic analyzer, 105 Herzog correction, 392 high-pressure mass spectrometry, 146 high-temperature vapors, 180, 245 Hopfield series, 402 hot band, 352 hot electrons, 265 hot-band effects, 180 hybridization, role, 10 hydrogen elimination, 498-500 hydrogen fluoride dimer cation,

dissociation energies, 151-2 equilibrium structure, 158-9 potential curve, 152 structure, 151-2

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hydrogen fluoride dimer, 109, 148-9 equilibrium structures, 113, 150

hydrogen fluoride dimer, ionization energies, 152-3 ionization, 138

1, 2-hydrogen shift, 201 hydrogen, 413

potential energy diagram, 489 hydrogen-bonded clusters, 110, 111 hydrogen-bonded dimers, 110

ionization, 102 hydrogen-bonded structures, 112 hydroxyl radical, 4-5

ICR photodissociation, 283, 291 IR fluorescence, 283 indirect double ionization, 329 interchannel coupling, 363 internal conversion, 532 intersystem crossing, 532 intracluster ion reactions, 245 iodobenzene ion, 281 ion character, role, 10 ion collection efficiency, 273 ion flight time, 276 ion fragmentation, 352 ion pair formation, 27 ion-molecule reactions, 162, 196 ion-neutral half-collision processes, 196 ionic character, 9

role, 14 ionization dynamics, 346 ionization energies, 170, 195, 215, 231

of 1, 2-difluoroethyl radical (X2A), 69 of 1-fluoroethyl radical (X2A), 57 of ammonia dimer, 149 of ammonia monomer, 149 of water dimer, 117, 128 of water dimer cation, 129 of water monomer, 117 of water monomer cation, 129

Jahn-Teller distortion, 20, 29 Jahn-Teller effect, 212

kinetic energy release distribution (KERD), 285, 307, 319, 332 kinetic energy release, 261-2 kinetic isotope effects, 528 kinetic shift, 24 Koopmans' theorem, 45, 52, 107

laser performance, 492 laser-induced fluorescence (LIF), 448, 488 laser-induced fluorescence, 234 lifetime broadening, 366

MCS coincidence circuit, 177 MPI, 72, 488 MPI-PES, 72-3 magic angle, 390 metal carbonyl photochemistry, 453

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metastable transitions, 204 methane, 46

PES of, 21 PIMSof, 21

methane, photoionization, 29 methanol dimer, 114, 120-1 methyl radical, 4-5, 45 microwave discharge, 5, 48, 50 microwave electrodeless discharge, 5 molecular beam photoionization, 216 molecular clusters, 506 molecular photoionization, synchrotron radiation probes, 373 molecular shape, 355 molecular-beam photoelectron spectrometer, 105 M0ller-Plesset perturbation theory, 48 Mulliken analysis, 54 multichannel detection, 354 multichannel quantum defect theory (MQDT), 389, 415, 470 multichannel sealer (MCS), 270 multiphoton excitation, 273 multiphoton ionization, 281 multiple photon multiple ionization, 304 multiple scattering method(MSM), 387-8 multiply charged ions, 299

neutral rare gas dimers, 216 NEXAFS spectroscopy, 360-1 nitrobenzene, 287 nitrogen fluorides, PIMS of, 13 nitrogen, 399 nitrous oxide, 420 non-Franck-Condon behavior, 357, 358-9, 365 non-hydrogen-bonded structures, 112 non-protonation, 136, 139 nonisotropic angular distribution, 290 nonlinear optics, 438 nonresonant autoionization, 329 nonstatistical decay, 285-7 nozzle beam source, 104

Ogawa-Tanaka series, 404 open-shell species, 45 optical multichannel analyzer (OMA), 354 organometallic compounds, 515 oscillator strength, 365 oxygen, 406 ozone, 45

p-p' exchange integral, 9 paralysis effect, 176 partial photoionization cross section, 347-9, 358 partial waves, 353 particle detection, 305-6 phase matching, 439, 440 phenetole, 274 phenyl ion, 281 phosphorus fluoride, PIMS of, 13 photoabsorption,

cross section, 4 spectra, 37, 504, 511, 517

photodissociation, 4, 242 cross section, 4

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photodissociative ionization, 20 photoelectron asymmetry, 366 photoelectron band widths, of water dimer, 128 photoelectron spectrometer, 47 photoelectron spectroscopy (PES), 2, 20, 106, 346, 348, 351, 353

of unstable molecules, 82-99 photoelectron spectrum, 2

of ammonia dimer, 114 of water dimer, 134

photoelectron-fluorescence coincidence (PEFCO), 259 photoelectron-photoelectron coincidence (PEPECO), 331, 337 photoelectron-photoion coincidence (PEPICO), 170, 216, 219, 259-61,

263-7, 273, 276-8, 283-4, 290, 292, 298, 315, 330, 333 apparatus, 173-6 spectra, 179, 217-31, 233-6, 238-47 TOF spectra, 176, 235

photoelectron-photoion-photoion coincidence (PEPIPICO), 259, 299, 302, 316, 321-5, 328, 334-7

photoelectrons, angular distribution, 475-7 photofragment spectroscopy, 448, 450 photoion yield, 12, 37

for boron hydride, 29 for vinyl radical, 25

photoion-fluorescence coincidence (PIFCO), 259, 321, 537 photoion-photoion coincidence (PIPICO), 299, 302, 316, 325, 332

apparatus, 317 spectra, 317, 322 spectral peak shapes, 319

photoionization efficiency (PIE), 170 spectra, 181-8, 190, 192, 195-9, 203, 206-7, 209-212, 217, 223, 229, 238-39, 243-4,247

photoionization half-reaction, 103 photoionization mass spectrometer, 171-2 photoionization mass spectrometry (PIMS), 2-7, 20, 106, 324

of ammonia dimer, 139 photoionization, 2

of high-temperature vapors, 180 spectrum, 2

photolysis with coherent VUV, 465-6 plasma desorption mass spectrometry (PDMS), 304 pnicogen hydrides, PIMS of, 9 polarization analyzer, 392, 396 polarization index, 526 polarization measurements, 508 polyatomic radicals, 248 polyatomic systems, 357 potential barrier, 201, 205, 357 potential-energy surfaces, of water dimer, 126 potential-energy surfaces, of water dimer cation, 123, 130 product correlations, 455 product orientation, 465 propensity rule, 413 proton transfer half-reaction, 102, 104 proton transfer, 162 proton-transfer process, 160 protonation, 136, 139 pseudo angle 390 pseudoreaction coordinate diagram, 201, 205, 214 pulsed differential coincidence scheme, 178 pulsed light source, 266 pulsed molecular beam, 274 pure covalency, 9

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pyrolysis source, 5 pyrolysis, 5

QET, 24 quantum defect theory, 388-9 quasiequilibrium theory (RRKM theory), 24, 278-80, 337, 528

R-dependent continuum coupling, 364 R-matrix method, 389 radiative cascading, 369 radiative lifetimes, 224, 228, 238 radical cation, appearance energy, 2 radicals, 242, 245, 247 random phase approximation (RPA), 380 rapid atom-molecule reaction, 44 reflection, 274 reflectron mass spectrometer, 307, 325 repulsive surface, 278 resistive anode, 395 resistive wedge, 394 resonance intramolecular charge transfer, 233 resonance line profiles, 187 resonance-enhanced multiphoton ionization (REMPI), 273, 370, 373, 488, 492-3, 497, 500 resonant autoionization, 466 resonant ionization, 349 resonant molecular photoionization, 346 resonant multiphoton ionization, 164 Ritz formula, 388-9 rotamers, 58 rotational cooling, 428 rotational energy, 274 Rydberg series, 10, 182-3, 186-7, 197, 268, 332, 513, 540 Rydberg states, 496

Schwinger variational calculations, 360 shape parameter, 187 shape resonance, 347, 355, 357, 359-60, 398, 424

polyatomic, 360-1 polyatomic nature, 372

shape resonant photoionization, 371 short-lived molecules, 44, 45

PES, 46 silicon (IV} hydride cation, structure, 23 silicon (iV) hydride,

PES of, 22 PIMS of, 22

silicon hydrides, PIMS of, 14 bond energies, 18 structure, 14

single-electron model, 380 six-wave mixing, 446 space charge effects, 304 space focusing, 270 spin polarization, 475 spin-orbit autoionization, 472 state-selective ionization, 495 statistical calculations, 455 statistical theory, 278, 280 stepwise radiative ionization, 191 steradiancy analyzer, 264, 266

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sublimation, 5 substituted benzene ions, 285 successive bond energies, 9 superexcited state, 234 supersonic expansion, 272 supersonic-beam technique, 107 synchrotron radiation, 216, 266, 299, 315, 346, 504-5 synchrotron, 72, 266, 270, 358

TOF mass spectrometer, 176 TOF spectrometer, 488 TPEPICO, 315 thermal energy, 260, 271-4 thermal pyrolysis, 242 third harmonic generation, 440 three-body reactions, 319, 326, 335 threshold electron analyzer, 265 threshold electron spectroscopy, 397 threshold electrons, 263, 269 threshold photoelectron spectrum (TPES), 266-8, 475 threshold photoelectron, 170 threshold photoelectron-photoion coincidence (TPEPICO),

263-4, 266, 267, 269, 277, 283, 286, 290, 298 time-of-flight (TOF) mass spectrometry, 248, 306 time-of-flight mass spectrometer, 3 time-of-flight photoelectron spectrometer, 72 time-of-flight spectroscopy, 468 time-resolved photoionization, 283 time-to-amplitude converter (TAC), 309 time-to-pulse height converter (TPHC), 269-70 total ionization rate, 260 transform-limited tunable lasers, 490 transient species, 2, 242, 247

generation of, 4-9 transition state switching model, 284 trichloro-, fluoromethane, 72 triple hydrogen bridge, 30 triplet-singlet ordering, 19

in SiH2, 16 tropyl ion, 280 tunneling mechanism, 161 two-body reactions, 334 two-photon resonant enhancement, 442

ultrahigh resolution laser, 491 ultraviolet photoelectron spectroscopy, 44 unimolecular reactions, 273, 496

VUV generation, 443 VUV laser, 3 VUV photoionization mass spectrometry, 170 Van der Waals cluster, 232, 246 Van der Waals dimer, 216, 232, 234 vaporization, 5 vector alignment, 457-8 velocity-aligned Doppler spectroscopy (VADS), 428, 460 vertical ionization energy, 45, 102, 107, vertically ionized point, 144 vibrational autoionization, 268 vibrational branching ratio, 349-50, 356-7, 359, 362, 365, 369 vibrational predissociation processes, 233 vibrational structure, 82-99

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vibronic coupling, 420 vibronic interactions, 406 vinyl cation, structure, 24 vinyl fluoride, 50, 261 vinyl radical, 24

structure, 24 virtual orbitals, 424-5

Wannier theory, 302 water dimer, 102-4, 108, 112, 114, 127-8

charge distributions, 133 equilibrium structure, 113 potential energies, 128

water dimer cation, 136 equilibrium structure, 158-9 potential-energy correlation, 137

Worley's third series, 404

ZEKE-PES, 72

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