Embed Size (px)
Citation preview
LIST OF PARTICIPANTS
Jose Luis M. ABBOUD Instituto de Quimica Fisica 'Rocasolano', CSIC, Serrano, 11928006 Madrid, SPAIN ([email protected])
Norman L. ALLINGER Computational Center for Molecular Structure and Design, Department of Chemistry, University of Georgia, Athens, GA 30602-2526, USA (allinger@sunchem. chem.uga.edu)
Robert 1. ANGELICI Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA (angelici@iastate. edu)
Peter B. ARMENTROlrr Chemistry Department, University of Utah, 315 S 1400 E R M Dock, Salt Lake City, UT 84112-0850, USA (arrnentrout(alchemistry.chem.utah.edu)
Lihn BACHE-ANDREASSEN Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, NORWAY (lihn. [email protected])
Nat,llia AVRAMENKO Chemistry Department, Moscow State University, Lenin's Hills, 119899 Moscow, RUSSIA ([email protected])
Tomas BAER Chemistry Department. University of North Carolina, Chapel Hill, NC 27599-3290, USA ([email protected])
BOlent BALTA Chemistry Department, Bogazi~i University, 80815 Bebek, Istanbul, TURKEY ([email protected])
John BARTMESS Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA ([email protected])
Irina BEREZINA VNIPIET, Dibunovskaya Street 55, St. Petersburg 197183, RUSSIA ([email protected])
Magda BIZARRO Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PORTUGAL ([email protected])
Olga BOLTALINA Laboratory of Thermochemistry, Chemistry Department. Moscow State University, Lenin's Hills, 119899 Moscow, RUSSIA (ovb(it)capital.ru )
Rui BORGES, Unidade de Ciencias e Tecnologias Agnirias, Universidade do Algarve, Campus de Gambdas, 8000 Faro, PORTUGAL ([email protected])
431
432
Michael T. BOWERS Department of Chemistry, University of California Santa Barbara, CA 93106, USA ([email protected])
Jerry CABALO Chemistry Department, University of North Carolina, Chapel Hill, NC 27599-3290, USA [email protected])
Violeta CALlAN Department of Physics, University ofCraiova, 13 A. I. Cuza, Craiova 1100, ROMANIA ([email protected])
Antonio CARMO Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL (a _ [email protected])
James S. CHICKOS Department of Chemistry, University of Missouri-St. Louis, St. Louis, Missouri 63121, USA [email protected])
Ion CIOCAZANU Department of Chemical Thermodynamics, University of Bucharest, Bd. Republicii 13, Bucarest 70031, ROMANIA ([email protected])
Anne COUNTERMANN Department of Chemistry, Indiana University, Bloomington, IN 47405, USA (acounter@indiana. edu)
Herminio P. DIOGO Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-00 I Lisboa, PORTUGAL ([email protected])
DilekDURAN Chemistry Department, Bogazi",i University, 80815 Bebek, Istanbul, TURKEY (durandil@boun. edu. tr)
Tereza FERNANDEZ Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PORTUGAL ([email protected])
Igor GALETICH Institute for Low Temperature Physics and Engineering, National Academy of Sciences of Ukraine, 47 Lenine Avenue, Kharkov 310164, UKRAINE ([email protected])
Nadezhda GALEVA Laboratory of Thermochemistry, Chemistry Department, Moscow State University, Lenin's Hills, 119899 Moscow, RUSSIA ([email protected] )
433
Rita GUEDES Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PORTUGAL ([email protected])
Camilla HAA VIK Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, NORWAY (camilla.haavik(i:l}kj emi. uio. no)
Steen HAMMERUM Department of Chemistry, The H. C. 0rsted Institute, University of Copenhagen, DK-2100 Copenhagen, DENMARK ([email protected])
Dorothea HILLESHEIM Departamento de Quimica, Faculdade de Ciencias, R. do Campo Alegre, 687, 4169-007 Porto, PORTUGAL ( [email protected])
Jens HENRIKSEN Department of Chemistry (lab II), The H. C. 0rsted Institute, University of Copenhagen, DK-2100 Copenhagen, DENMARK ([email protected])
Karl K. IRIKURA Physical and Chemical Properties Division, National Institute of Standards and Technology, 22I1AIII, Gaithersburg, MD 20899-0001, USA ([email protected])
Pilar JIMENEZ Instituto de Quimica Fisica 'Rocasolano', CSIC, Serrano, 11928006 Madrid, SPAIN (rocjimenez(il}roca.csic.es)
Russell JOHNSON National Institute of Standards and Technology, 22I1AIII, Gaithersburg, MD 20899-0001, USA (russell.johnson(il}nist.gov)
Cengiz KA V AKLI Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, TURKEY ([email protected])
Tetsu KIYOBA Y ASHI Osaka University, Microcalorimetry Research Center, Faculty of Science, Toyonaka 560-0043, JAPAN ([email protected])
Rick LAFLEUR Chemistry Department, University of North Carolina, Chapel Hill, NC 27599-3290, USA ([email protected])
Ana Lucia C. LAGOA Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-00 I Lisboa, PORTUGAL ([email protected])
Joao Paulo LEAL Departamento de Quimica, Instituto Tecnol6gico e Nuclear, Estrada Nacional N° 10, 2686-953 Sacavem, PORTUGAL ([email protected])
434
Dale LEV ANDlER Air Force Research L1b, AFRUVSBM, 29 Randolph Rd., Hanscom Air Force Base, MA 01731-3010, USA ([email protected])
Joel F. LIEBMAN Department of Chemistry and Biochemistry, University of Maryland Baltimore County, 1000 Hilltop Circle, Baltimore, MD 21250, USA ([email protected])
Joaquim MAR<;ALO Departamento de Quimica, Instituto Tecnol6gico e Nuclear, Estrada Nacional N° 10, 2686-953 Sacavem, PORTUGAL ([email protected])
Nadine MARCHANDE GRECH) - Chimie Physique Organique, Universite Nice Sophia Antipolis, 06108 Nice CEDEX 2, FRANCE ([email protected])
Jan M. L. MARTIN Department of Organic Chemistry, Kimmelman Building, Room 262, Weizmann Institute of Science, IL-76100 Rechovot, ISRAEL (comartin(G}wicc. weizmann.ac.il)
Konstantin MARUSHKIN Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky pr. 31, 117907 Moscow, RUSSIA ([email protected])
Yuksel MERT Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, TURKEY ([email protected])
Aristophanes METROPOULOS National Hellenic Research Foundation, 48 Vass. Constantinou Ave., 11635 Athens, GREECE ([email protected])
Terrance B. McMAHON Department of Chemistry, University of Waterloo, Waterloo, Ontario, CANADA N2L 3G 1 (mcmahon@uwaterloo. ca)
Margarida MIRANDA Faculdade de Ciencias d,1 Universidade do Porto, Departamento de Quimica, R. do Campo Alegre, 687, 4169-007 Porto, PORTUGAL ([email protected])
Magdalena MOMIRLAN Institute of Physical Chemistry, Spl. Independentei 202, Bucharest 77208, ROMANIA ([email protected])
Manuel Joao MONTE Faculdade de Ciencias da Universidade do Porto, Departamento de Quimica, R. do Campo Alegre, 687, 4169-007 Porto, PORTUGAL ([email protected])
Peter MULDER Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, 2300 RA Leiden, THE NETHERLANDS ([email protected])
Yatsuhisa NAGANO Osaka University, Microcalorimetry Research Center, Faculty of Science, Toyonaka 560-0043, JAPAN ([email protected])
Steen Broendsted NIELSEN
435
Department of Chemistry (lab II), University of Copenhagen, The H. C. 0rsted Institute, University of Copenhagen, DK-2100 Copenhagen, DENMARK ([email protected])
George NIP AN Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninsky pro 31, 117907 Moscow, RUSSIA ([email protected])
Paulo NUNES Escola Superior Agniria de Santarem, S. Pedro, Apartado 310, 2004 Santarem Codex, PORTUGAL (d683@beta. ist.utl.pt)
Cemil (')GRETIR Osmangazi University, Faculty of Arts and Sciences. Chemistry Department, Eskisehir 26470, TURKEY (cogretir@ogu. edu.tr)
Patrick A. G. O'HARE Physical and Chemical Properties Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-0001, USA ([email protected])
Maria da Concei~1io OLIVEIRA Centro de Quimica Estrntural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL (pcmcoli [email protected])
Jennifer ORF University of Missouri-St. Louis, 8001 Natural Bridge Rd., St. Louis, Missouri 63121-4499, USA
Victor OSTROVSKII Karpov Institute of Physical Chemistry, ul. Vorontsovo Pole 10, Moscow, 103064, RUSSIA (vostrov@cc .nifhi .ac.rn)
I. Tamerkan OZGEN Izmir Institute of Technology, Gaziosmanpasa Bulv., 16 Cankaya, Izmir 35210, TURKEY (ozgen@triyte. iyte. edu. tr)
Nikos PAPADOPOULOS Laboratory of Physical Chemistry, Department of Chemistry, University of Thessaloniki, Thessaloniki 54006, GREECE ([email protected]. gr)
Stefan PERISANU Laboratory of General Chemistry, Polytechnic University of Bucharest, Str. Polizu 1, Bucarest 78126, ROMANIA (s yerisanu(alchim.upb.ro)
436
Allan Christian PETERSEN Department of Chemistry (lab II), The H. C. 0rsted Institute, University of Copenhagen, DK-2100 Copenhagen, DENMARK ([email protected])
Manuel E. MIN AS DA PIEDADE Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL ([email protected])
Krzysztof PIELICHOWSKI Department of Chemistry and Technology of Polymers, Technical University, ul. Warszawska 24, 31-155 Krakow, POLAND ([email protected])
Anamaria POPESCU Romanian Academy, Institute of Physical Chemistry, Laboratory of Molten Salts, Spl. Independentei 202-Sector 6, Bucarest 77208, ROMANIA ([email protected])
Maria das Dores RIBEIRO da SILVA Faculdade de Ciencias da Universidade do Porto, Departamento de Quimica, R. do Campo Alegre, 687, 4169-007 Porto, PORTUGAL ([email protected])
Mary T. RODGERS Wayne State University, 5101 Cass Ave. 33 Chemistry, Detroit, 48202, USA (mrodgers@chem. wayne. edu)
Victoria ROUX Instituto de Quimica Fisica 'Rocasolano', CSIC, Serrano, 11928006 Madrid, SPAIN (rocvictoria(GJroca.csic.es)
Chad RUE Chemistry Department, University of Utah, 315 S. 1400 E., R M Dock, Salt Lake City, UT, 84112-0850, USA (chad@chemistry. chem. utah.edu)
Malgorzata WSZELAKA-RYLIK Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, POLAND ([email protected])
Bekir SALIH Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, TURKEY ([email protected])
Rui C. SANTOS Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL ([email protected])
Cenk SEL<;UKI Chemistry Department, Bogazi~i University, 80815 Bebek, Istanbul, TURKEY ([email protected])
Nurcan SENYURT Chemistry Department, Bogaziyi University, 80815 Bebek, Istanbul, TURKEY (senyurtn(il)boun.edu.tr)
437
Jose A. MARTINHO SIMOES Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PORTUGAL ([email protected])
Bernd SCHROEDER Institute fur Anorganische Chemie, Talstr. 35, Leipzig 043 17, Germany (stuinorg@organik. orgchem.uni-Ieipzig.de)
Luis Carlos SILVA Faculdade de Ciencias da Universidade do Porto, Departamento de Quimica, R. do Campo Alegre, 687, 4169-007 Porto, PORTUGAL ([email protected])
Palmira SILVA Centro de Quimica Estrutural, Complexo Interdisciplinar, Im,tituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL ([email protected])
George STOENESCU Department of Physics, University ofCraiova, 13 A. I. Cuza, Craiova 1100, ROMANIA ([email protected])
Clementina TEIXEIRA Centro de Quimica Estrutural, Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisboa, PORTUGAL (pcclementina(iljalfa. ist. utI. pt)
Mats TILSET Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, NORWAY ([email protected])
Nesrin TOKAY Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, TURKEY (ntokay(ti)eti. ce. hun. edu. tr)
lwona TOMASZKIEWICZ Institute of Physical Chemistry, Polish Academy of Sciences, UI. Kasprzaka 44/52, 01-224, Warsaw, POLAND ([email protected])
Wing TSANG Physical and Chemical Properties Division, National Institute of Standards and Technology, Gaithersburg, MD 20899-0001, USA ([email protected])
Canan ONALEROGLU Department of Chemistry, Hacettepe University, Beytepe Campus, 06532 Ankara, TURKEY (canan@eti. cc. hun. edu.tr)
Ellie L. UZUNOV A Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., block 11, Sofia 1113, BULGARIA ([email protected])
438
Eric WEITZ Department of Chemistry, Northwestern University, Evanston, Illinois 60308-3113, USA (weitz(l'l)nwn.edu)
Miijgan Y AMAN Osmangazi University, Faculty of Arts and Sciences, Chemistry Department, Eskisehir 26470, TURKEY ([email protected])
SUBJECT INDEX
A
Ab initio 196,245,265,267,270-272,297,314, 316-318,353-372,418,419,421 Absolute bond energy 161 Abstraction reactions 332, 343 Acetonitrile as a solvent 164 Acid-base reaction 79 Acidic aqueous solution 276 Acidities 8, 10
of cationic hydrides 164 Acidity 10,266
Gas phase 305 Acoustic wave 138,219 Activation barrier 19,333 Activation energies 16,23,25,312,317,333, 336-338,341,348-349 Adiabati c calorimeter 55 Adiabatic electron affinity 10, 12, 21 Adiabatic expansion coefficient 139, 141, 148 Adiabatic ionization energy 7,8, 19-20 Adiabatic photocalorimeters 115 Adiabatic temperature rise, I1Tad 114 Adduct ion 268-269 Additivity of bond energies 417 Adsoption 153 Algae Chiarella 108 Arninoquinolines 207 Anharmonicity 385 Anharmonicity constants 386 Aneroid calorimeter 32 ANO basis sets 380 Anodic peak 156,160 Antiaromatic 45-46 Apparentltdonation 170,172-173 Appearance 251 Appearance energy 7,19,267 Aqueous normal hydrogen electrode 156 Aromatic 45-46 Arrhenius activation 23 Arrhenius parameters 16, 22, 278-279
Non-Arrhenius character 348 Arrhenius plot 338,340
Negative curvature 348 Arrival time distribution, ATD 239 Arsenious oxide 39-40 Association reaction 268, 270 Asymmetric reactions 272 Atom equivalent schemes 374 Atomic radical 348 Atomization energy 373.384,387.397
OfSiH4 400 OfBF 405 OfBF, 401-406
Azobenzene, cis-trans isomerization 127-129
439
B
Backbonding 246 B3LYP 142,358,362,364 BAC-MP4 358,363-364,374 Band path 120 Barrier height 272, 275 Basic complexes 77, 98 Basicity 266 Bath gas 260, 261 BD 379 BDT 379 BD(T) 379 Basis set 355,379-381
6-3IG* 420 6-3IG(d) 355 6-311G** 382 6-311 +G( d,p) 362, 363 6-311+G(2df,p) 382 6-311++G(3df,2pd) 382 Atomic natural orbital 380-381 ACVQZ 398,404 ACV5Z 398 AVDZ 382 A VQZ 382,398,402 A V5Z 397-398,402 A V6Z 382,398,402 Aug-cc-pV5Z 394 cc-p V5Z 384, 390 cc-pCVnZ 383,384,390 cc-pCVTZ 383 Correlation consistent 364, 379 Martin-Taylor core correlation
383-384 Basis set superposition error, BSSE 387 Benson's estimation method 317,354,361-362 Benzene, hydrogenation 30 Benzoic acid 30,34-35,39,62 Bimodal distribution 245 Bimolecular exchange reaction 264 Bimolecular reaction 266 Binding energies 241,245,248,250 Binding energy 272 Binding enthalpy 275 Birge-Sponer extrapolation 2 Black body 277 Black body radiation 279 Boil ing temperatures 206 Boltzmann distribution 260,277,327,422 Boltzmann statistics 20 Bomb calorimetry 304-305 Bomb process, chemistry of37-41 Bond breaking step 311,333 Bond cleavage reaction 279,338,340,348
Homolytic 308
440
Bond dissociation energy 1-28,153,161,164, 170,172-174,215,221, 279,341,343,360
Bond dissociation enthalpy, BDE 1-28,43,55, 71, 131, 137-138, 141-143,146-149
C-H 143, 149, 165 O-H 144,148 R-H 141-142 of organic compounds 138 organometallic compounds 138
Bond dissociation Gibbs energy 5, 9 Bond energies 215,221,227,304,323,325-326,
328,331-332,338-339, 341,347,349-350
Bond energy 247,249 Bond energy terms 417,419 Bond enthalpy 308 Bond weakening 168 Bonds, C-C 422 Bonds, C-H 422 Bond strength 269 Born-Oppenheimer 356 Bracketing 84 Bracketing method 10, 13 Br0nsted base 77 Brueckner orbitals 379 t-butoxyl radical 144-145, 148-149
c C60 47,48 C70 47,48 Calibration of calorimeter 34-35,62 Calibration constant 114, 119 Calorimeter proper 32-35 Calorimeter-spectrophotometer 108 Calorimeter-photometer 108 Calorimetric absorption spectroscopy 109 Calorimetric transmission spectroscopy 109 Carbons, Quaternary 421
Tertiary 421 Carbonyl ligands 77,92,95-98 Carbonyls 218 CASSCF 379 Catalytic chemical process 227 Cathodic peak 156, 160 CBS methods 374 CBS-Q method 363 CBS-Q 374 CBS-QCI/APNO 374 CCSD 355,377,379,395 CCSDT 382,394 CCSD(T) 355,356,364,379,382,391,
393-395,398,401 Charge transfer 248 Chelate ligand 89 Chemical equilibrium 262
Chemical ionization 260-262, 293 Chemical kinetic modeling 331 Chemical trapping 225 Chlorohenzene, enthalpy of formation of
359-360, 363-364 CISD 355,375,377,379-380 CISDT 375 Classification of photocalorimeters 109 Clausing factor 204 Clausius-Clapeyron equation 186,205 Cluster assisted insertion 250 Cluster assisted mechanism 247-248 Cluster assisted sigrna bond activation 249 Cluster expansion 376 Cluster ion 237,276,279 Clustering 262, 265 Clustering reaction 262 Clusters 235 CO2 analysis 30, 42 Coherent lCR motion 288 Coherent motion 286 Collision complexes 236 Collision frequency 260 Collision induced decomposition, CID 11, 13,
243, 290, 298-299 Collision induced dissociation, CID 242-243 Collisional stabilization 260 Collisionallyexcited 236 Collisions 262 Combustion aid 64 Combustion calorimetry 3 Combustion calorimetry in oxygen 29-54, 129
Moving-bomb 29,38-42,44 Micro 30, 48-49 Reaction-solution 44-45,62 Static-bomb 29,40,42,44
Comparative rate technique 332,335,344 Comparison experiments 36,41 Complete basis set method 359 Computational chemistry 43,47,49,353 Concentrations vs. time 14, 16 Concentrations vs. time at several temperatures
14,22,24 Configuration interaction, Cl, FCI 375,377,382 Connectivity-based schemes, 374 Coordinatively unsaturated metal carbonyls
Conjugate base 261 Cooks method 298
215-234
Correlation consistent basis sets 364, 379 Correlation energy 359 Correlation gas chromatography 185, 189, 191,
195-196 Counter electrode 154 Coupled-cluster theory, CC 355,376-377 Covalent adducts 269 Covalently bound adduct 268 Covalently bound protonated structure 268
Cross section 262 Cyclic voltametry, CV 5,153-157,165,167 1,5-cyclooctadiene 77 Cyclopentadienylligand, Cp 95,97-99,239
Substituted cyclopentadienylligand 95-98
Cyclotron frequency 282-284 Cyclotron motion 285 Cyclotron orbital phase 286 Cyclotron orbits 283 Cyclotron 282 Cylindrical lens 261
D
Daughter ion 290, 315 Decay rate 317
Two-component 318 Decomposition 332
Channel 340 Rates 345
Deconvolution 308 Degree of freedom 268 Deprotonation 298 Densities of states 253,317 Density functional method 138,354,356,365,
374,417,419-423 B3L YP 356,358,362,364
Detection electrodes 284 Dewar-Chatt-Duncanson model 223 1,2-dichloroethane (DCE) 78,80-84,91,96 Dichlorosilane, enthalpy offormation of 361,
363-364 Differential charge 286 Differential heat input vs. temperature or time 4 Differential scanning calorimeter (DSC) 108 Differential scanning calorimetry (DSC) 4, 191 Diffusion 153 Diffusion-controlled radical dimerization 160 Diffusion-controlled reaction 15 Diffusion layer 154, 157 Diffusion process 262 Digital simulation of cyclic voltammograms
154, 160 Dihydrogen ligands 247 Dipole moments 272 Direct clustering 268 Dissociation limit 313 Dissociation rate 306 Dissociation reactions 277, 318 Dissociation step 277 Dissociative ionization 306,309,312-313
Onsets 3 I I, 313 Dissociative photoionization 304 Distonic ion 3 I 6-318 di-t-butyl peroxide 140,142-144,146 DNA repair 46 DNA photolyases 46
Donor-aceptor bond 77 1t donors 169 1t donors 131 Double helix 46 Double-layer charging current 157,160 Double resonance 294 Dppe 77 Dual cells 285 Dynamical correlation effects 379
E
Effective core potentials 358
441
effects on ionicity of the M-X bond, cr and 1t 169 Effusion 203-204, 208
Mass-loss 203-204, 207 Torsion 203-204,207 Hole 204-205 Time 204 Cell 204-205 Static method 205
Diaphragm manometer 205
Spinning rotor 205 Techniques 208
Electric field 281, 3 14 Electrical pulse 309 Electrochemical cycle 138 Electrochemical measurements 5 Electrochemical methods 153-176 Electrochemically irreversible 159 Electrode potential 153, 173 Electromagnets 286 Electron affinity, EA 8,19,161,295,299,381,
398-399,303-306,310 Electron attachment 21, 261 Electron attachment Gibbs energies 13 Electron beam 260 Electron configuration 244 Electron count vs. electron kinetic energy 19 Electron donating 84 Electron exchange 295 Electron gun 260 Electron impact 244, 26 I Electron impact mass spectrometry 7 Electron ionization 238,295 Electron photodetachment spectroscopy 7,306 Electron releasing 85-86,96 18-electron rule 77 Electron transfer 248 Electronic effects 266 Electrospray 289 Electrostatic attraction 246 Electrostatically bound 271 Empirical atom equivalents 358 Empirical corrections 374 Empirical correlations 203 Energetics 235
442
of heterolytic metal-ligand cleavage 153
of homolytic metal-ligand cleavage 153
Energies 10 Energy of combustion 40 Energy equivalent 34,36, 114 Energy exchange 277 Energy levels 314 Energy state distributions 238 Energy threshold 312 Enthalpy of activation 14,15 Enthalpy change 262, 272 Enthalpy offormation 29,32,43-44,47-49,55,
129,177,296,203,325, 354,357,359,373
Gas phase 177 OfB 401 OfSi 400
Enthalpy of fusion 177-202, 183, 189 Enthalpy of reaction 79,80, 105, 127, 129-130,
140-141, 145,323,354, 357
Apparent 141 Enthalpy of solution 128 Enthalpy of sublimation 177-202,203-205,207-
212 Apparatus 182 of anthracene 182 ofcoronene 177,189-190,195-197 by C-GC 188, 195 by DSC-CGC 189-190 ofperylene 177,190,195-197
Enthalpy of transfer from solution to the vapor 187
Enthalpy of vaporization 177-202, 206 Entrance channel complex 271 Entropy change 262, 268, 272 Entropy of association 269 Entropy of formation 325-326 Entropy of sublimation 203,206,210 EPR 9,15 Equilibrium 274,291
Concentrations 8, 9 in solution 9 in th e gas phase 8 Thermodynamic 330
Equilibrium constant 77-79,253,262,297,304-305, 323-327, 345
Equilibrium pressure 204-205 Equilibrium studies 284 Estimation of phase change entropies 191,194 Ethylene 223 Exchange reaction 271 Excitation electrodes 284-285 Excitation power 291 Excited state 246, 250 Exit channel complex 271
Exit channel well 272 Exponential decrease 287 External ion source 239,289 Extrapolation to the infinite-basis limit 390-398 Eyring plot 14-15
F
Faradaic current 157 Fast atom bombardment, F AB 289 Fermi-Dirac statistics 20 Ferrocene 141,156 Field ionization 310 First order exponential decay 277 First-order reactions 158-159 First row 244 First solvation shell 245,248 Flash photolysis 216 Fluorine bomb calorimetry 55-76 Flowing Afterglow - selected ion-flow tube 10 Force field methods 355 Fourier transform 218 Fourier transform infrared spectroscopy, FT -[R
9,15,218 Fourier transform ion cyclotron resonance spectroscopy, FT-[CR 261,276-279,281-282,
284,287,289,291,294, 297,299
Franck-Condon factors 306-308 Fragment ion 311,330 Fragmentation 293 Free electrons 309 Free energy of fonnation 325 Free radicals 303,305,310 Frequency-domain magnitude 287 Fullerenes 47 Fusion enthalpies 177-178,189,191-192,196 Fusion entropies 177
G
Gl method 384 G2 method 359,363,374,376-377,382,384 Gas phase acid strength 261 Gas phase acidity 12, 138,266,296 Gas phase heat offormation 143 Gas phase acids 261 Gas phase affinity 298 Gas phase basicity 261,266-267,296,298 Gas phase ions 235 Gas phase photolysis 220 Gas phase SN2 reaction 270 Gas phase studies 216,228 Gaseous cluster ions 268, 277 Gaussian 94 program 422 Geometric isomer 239,251 Geometry changes 306 Geometry optimization of the molecule 422
Glow discharge 238 Glow discharge ion source 244 Gorin loose transition state 349 Graphite 59 Ground state 236, 247-248, 250 Groupadditivitymethods 177,180-181,191,
193 Group equivalents 421 Group methods 180,196,355 Guided ion beam mass spectrometry \0
H
H2 elimination 250 Halide exchange 295 Halide ligand 94 Halide transfer 264 Halogen cation exchange 295 Hammett acidity 81 Hammett constant 148 Hartree 357 Hartree-Fock, HF 355-356,359,362-363,375,
417,419-423 Heat capacity 20-21. 23,119,139,180,206-207,
326,341 Estimated 181,189 Gas phase 179-180,185 Liquid phase 180, 184 Solid phase 179, 184
Heat conduction calorimeter 108, 119 Heat conduction photocalorimeter 115 Heat of combustion 304,325 Heat of dilution 81,83 Heat offormation 137-138, 143, 149,303-304,
309,318,326,328,339, 342-343,349-350
By density functional theory 417-429 By molecular mechanics 419,422 Of organic molecules 313,417-420,
422-423 Of saturated hydrocarbons 419,422-
423 Free radicals 303,323-324,341
Heats offormation of ions 235 Heat of protonation 83-86, 164 Heat of reaction 78,79,81,83,304 Heat of sublimation 203 Hess's law 303,304 Heterogeneous electron transfer 153, 159-160 Heterolytic bond cleavage 161,173 Heterolytic cleavage 99 HF/6-3 I G(d) model 355,359,360-362 High pressure ion source 264, 279 High pressure limit 218,337-338 High pressure mass spectrometry, H PMS 11,
259,264, 266,270-272, 275,297,305
High pressure rate constant 323
High resolution 288 High temperature mass spectrometry 15 High temperature reactor 338 Homodesmic reaction 361,373 Homodesmotic stabilization enthalpy 45 Homodesmotic reaction 46 Homogeneous chemical reactions 153,158 Homogeneous relaxation 287
443
Homolytic bond dissociation energy 161, 173 Hybrid correction/extrapolation schemes 374 Hybridization 246 Hydrazine hydrochloride 39,40 Hydride affinity 12, 19 Hydride exchange 295 Hydride ligand 94 Hydrogen abstraction 144-149 Hydrogen bond 142,144-145 Hydrogen bonding 82-83 Hydroxiquinolines 207 p-hydrogen transfer 225,228 2-hydroxybenzophenone 140
I
ICR orbital motion 286 ICR orbital radius 287 ICR 282-283,287,291,296-297,305 Infrared absorption cross-sections 227 Infrared diode laser 216 Inner shell polarization 380,382,384 Inner shell correlation 383 Inorganic compounds 41,57
Arsenium 59 Germanium 59,71-73 Iodine 59 Phosphorus 59 Sulfides 56 Sulfur 59 Selenium 59 Silicon 59 Telurium 59 Uranium 59
Inserted products 247 Insertion 247,248 Internal energy 277, 306-307, 312-313, 316-317
States 306-307 Internal rotations 265,269
Barrier to 346 Internal standard 336 Intersystem crossing 138 Intrinsic reactivity 293 Ion beam methods 236 Ion chromatography 239,244,251 Ion convention 20 Ion cyclotron resonance 8 Ion cyclotron resonance mass spectrometry 12 Ion detection 283 lon-dipole interaction 271
444
Ion dissociation 316 Ion dissociation dynamics 303 Ion energetics 259 Ion equilibria 238 Ion equilibrium measurements 235 Ion excitation 283 Ion-induced dipole interaction 271 Ion intensities 10-12,17,19,21,293
vs. electron energy 7, 12 vs. ion kinetic energy 10 vs. photon energy 7, 12, 19 vs. product kinetic energy 13 vs. temperature 15 vs. time 10, 12
Ion lifetime 312 Ion-molecule collisions 282 Ion-molecule reactions 266 Ion-neutral pair 275 Ion pair states 314 Ion-pairing effect 83-84, 86 Ion selection 289 Ion source 238,262 Ion trapping 282, 289
Time 312 Ionization 13
Collisional 313 Ionization agents 261 Ionization cross-section 307 Ionization energies 21 Ionization energy 10, 19,304,306-308,310,
314,316 Radicals 303-304 Adiabatic 310
Ionization onset 306-308 Ionization potential 161,262,293 Ionization region 309-310 Ionization threshold 308 Ionic chromatography 41 Ionic dissociation 312
Slow 312 IR spectra 92 Irradiation systems in photocalorimetry 121 Irreversible process 160 Irreversible oxidation 168 Iron hydrogen bonds 224 Isentropic process 330 Isobaric expansion coefficient 139 Isodesmic reaction 360, 362, 373, 419 Isogyric reaction 359,360 Isomerization 268,311,313,318,338
Ofazobenzene 127 Barrier to 316
Isomerization barrier 251-252 Isomerization process 226 Isomerization rate constants 253 Isoperibol 23 Isoperibol calorimeter 32, 34 Isoperibol photocalorimeter 113-115
Isothermal 23 Isothermal calorimeters 115
K
Kinetic energy 236, 290, 315 Kinetic energy release distribution, KERD 13,
236-237,239,242 Kinetic energy release measurement 237,307,
311,315 Kinetic measurements 327 Kinetic potential shift 158,160 Kinetics 215
Gas phase 14 Solution 14
Kinetic shift 19-20,312 Kirchhoff's equation 179 Knudsen cell - Mass spectrometry 15, 204 Knudsen cell measurements 128 Knudsen effusion 203-204, 207
L
Laser ablation 264-265 Laser beam 139 Laser calorimetry 109 Laser desorption, LD 238,289 Laser excitation 309 Laser flash photolysis (LFP) 146 Laser intensity 141 Laser-powered homogeneous pyrolysis 16 Lewis acid 98 Lewis base 98 a-ligands 169, 172 Ligand association process 223 Ligand Association Reactions 218 Ligand effects 86, 248 Ligand influences 219 Light guides 106 Light induced processes 105 Light source 309
Pulsed 309 Lindemann mechanism 277 Linear anharmonic oscillator model 3 Lone pair 270 Luminiscence processes 106
M
Macrocombustion calorimetry 29 Macromolecular folding 251 Macromolecular systems 251 Macromolecules 235 Magnetic field 281,284,286,290 Magnetic sector 261 Magnetron motion 285 Mass analysis 261
Mass analyzed laser desorption ionization, MALDI 238,295 Mass analysed threshold ionization, MATI 310 Mass effusion rate 204 Mass spectrometry - kinetic method 17,323-
324,328 Mass transfer 154 Matrix interactions 223 Matrix isolated molecule 225 Matrix isolation techniques 215 MBPT 377 MBPT2355 MBPT4355 MBPTn 376 Mechanism of reaction 238 Mean bond dissociation enthalpies 22 Mean free path 205 Melting point 190-191 Metal basicity 86-89,93-94,98 Measured pressure 205 Metal carbonyls 221,227 Metal cation exchange 295 Metal cation transfer 264 Metal centers 227 Metal cluster ions 265 Metal-hydride acidity 162-163 Metal-hydride bond dissociation energies 161,
165,171,173 Metal-hydride cation radical acidities 165-167 Metal-hydride cation radical bond dissociation
energy 167-169 Metal hydride complex 77, 99 Metal-hydride homolytic bond energies 173 Metal-hydride oxidation 166 Metal-hydrogen bond dissociation energy 99 Metal hydrogen bonds 223 Metal ion complexation reaction 79 Metal-ligand bond 153 Metal ligand interactions 248 Metal-metal bond 97-98 MeL1Stable complexes 237 Metastable excited states 239 Methyl cation transfer 264 Microcalorimeters 112 Macrocalorimeters 112 Microcombustion calorimetry 30, 42, 47 Mn-CO bonds, cleavage of 130 Mobility 239 Molecular flow 204 Molecular orbital method 354 Molecular mechanics 374,417,419,421-423 Molecular structure 180 Molecular ions 303 Molybdenum silicide 56 Monochromator 120 MP2 355-356,362-363,382,393-394 MP4355-356,358,382 MPn 376
Multiphoton absorption 216 Multiply charged ions 289
N
Nd:YAG laser 216 Nearly degenerate orbitals 235 Near-Nerstian process 160 Negative entropy changes 272 Negative ion formation 261
445
Negative temperature dependence 249,275,343 Nernst equation 155 Neutral precursor 310 Neutral species in the gas phase 299 Neutral structures 313 NMR spectroscopy 9, 15,78,98 Non-Faradaiic current 157 Non-Nernstian electron transfer 159 Nucleophilic attack 270 Nucleophilic displacement 270
o Olefin binding 223 Olefin formation 250 Olefin isomerization 224 Open-shell systems 377 Operation of photocalorimeters 122-126 Optical irradiation systems 120 Organic compounds 29-30, 57
Containing boron 40 Containing chlorine 39-40 Containing CHO 37 Containing CHON 37 Containing bromine 39-40 Containing fluorine 39-40 Containing iodine 40 Containing phosphorus 41 Containing selenium 38 Containing sulfur 38 Halogenated 39
Organometallic compounds 29,41-43,49 Bis-cyclopentadienyl transition metal
43,45 Organometallic ligands 7,81 Organometallic superacids 166 Oxidation 156,160 Oxidation potential 162-163, 165 Oxidation-reduction reaction 79 Oxidative activation ofM-H bonds
p
Parameter, FTX 131
168
Parametrized configuration interactions, PCI 359 Parent ion 289-290 Partially reversible 160
446
3PC 374 PC/-X 374 Peak center frequency 286 Peak height 286 Peak potential 160 Peak width 286 Pentacarbonyls 223 Perturbation theory 355 pH glass elctrode 78 Phase change enthal py 183 Phenol 140, 145 Phosphine ligand 86-93,98-99 Photoacustic calorimetry, PAC 17,109,130,
137-1375 Photoacoustic signal 17,138-141,144,146 Photoacoustic spectroscopy 108, 138 Photobromination of hydrocarbons 108 Photocalorimetric spectroscopy 109 Photocalorimetry 18, 105- I 36 Photochemical quantum yield 140, 142, 146 Photochemical reaction 106 Photochromic systems 127 Photodegradation 105, 108 Photodetachment spectroscopy 304 Photoelectron photoion coincidence, PEPICO
306,311-312,314,316 Photoelectron spectroscopy 19,307-309
Negative ion 310 Photoinduced chemical process 137 Photoinitiated process 138, 141 Photoionization etliciency curve 19 Photoionization mass spectrometry 19,138,307,
309 Photoionization thresholds 343 Photolysis radiation 216 Photolysis wavelength 221 Photomodulation voltametry 5 Photon density 277 Photon energy 307-308,312,314 Photon transition 308
One- 308 Photopolimerisation 105, 108 Photosubstitution of carbonyl in
Mn(ljj CjH4CH3)(CO)3 130-132 Photosyntesis 105, 108 Photothermal beam deflection spectroscopy 109 Piezoelectric sensor 139-140 pKa 6,78,83-84,92,98,131,153,161-163 Polarizability 272 Polycyclic hydrocarbons 207, 211 Potassium ferrioxalate as a calibrant in
photocalorimetry 126-127 Potential energy profiles 266,274-275 Potential energy surl'lce 239,250,271-272,311,
318,348 Precipitation reaction 79 Pressure wave 138-139 Probe beam det1ection 138
Product structures 3 \3 Promotion energies 245 Propene 225 Proton abstraction 261 Proton affinity 8, 17, 19,266-268,296,305 Proton bound dimer 262, 298 Proton exchange reactions 291 Proton exchange 294 Proton sources 293 Proton transfer 261,264,266,268,270,291,
294,305 Proton transfer equilibrium 163-164, 166, 267 Protonated base 270 Protonation reaction 90,97-98 Protonic basicities 293 Pseudo first order 272 Pulse sequence 288 Pulsed field ionization 314 Pulsed field ionization/zero kinetic energy, PFIIZEKE 309-310 Pulsed high pressure mass spectrometry 21 Pulsed laser photocalorimeter 109 Pyracylene 45-46 Pyrimidines 46 Pyroelectric photocalorimeters 108 Pure extrapolation methods 374
Q
QCISD 377 QC1SD(T) 377,382 Quadrupolar static electric potential 284 Quadrupole electrostatic potential 285 Quadrupole mass filter 311 Quantum mechanical methods 417,422 Quantum yield 18, 107 Quasi-adiabatic photocalorimeter 113-115
R
Radiation exchange 291 Radiation hypothesis 277-278 Radiation mechanism 277 Radiation step 277 Radiative decay 140 Radicals 137,323,325,328,335,338-339, 343,
345,349 Scavengers 327 Lifetime 334 Recombination 338,344-345 Buffer 344 Decomposition 348
Radiolysis 259 Rapid scan 218 Rate of absorption 279 Rate equation 332-333 Rate constant 10,25,215,227,252,266,271-
272,279,305,315,318,
323,327-328,331-332, 335-337,340,343-344, 348
Abstraction 333 Bimolecular 327 Dissociation 312 Reverse 341 Recombination 345 Unimolecular 335
Reaction channels 237 Reaction cross-section 219 Reaction enthalpy 305 Reaction ell.ient 335 Reaction mechanism 215,224,327,339 Reaction-solution calorimetry 22, 128, 130 Reaction states 303 Reaction temperature 331 Reactive intermediates 303, 330 Rearrangement 316 Redox potential 5-7,98, 161
Reversible 5 Reduction 156, 158 Reduction potential 5 Reference elctrode 154, 156, 162 Reflected shock 332 Regeneration ofa parent ion 221,228 Relative acidity 293,296 Relative basicity 296 Relative bond energy 161 Relative metal-X bond dissociation energies
169-173 Relativistic effects 358,388-176 Relaxation 288 Repulsion 246 Residence time 286,333,335,337 Retention time 185-186 Reverse activation energy 310, 313, 326 Reverse activation barrier 20,237-238,307 Reverse Diels Alder 340 Reverse reaction 338 Reverse recombination 348 Reversible electrode potentials 170 Reversible oxidation 155-156 Reversible process 170 Rigid rotor-harmonic oscilator 386 Rotating monopole 284 RRKM theory 25,303,312,314,316,318 Rydberg series 314 Rydberg states 309,314
s Scalar relativistic contribution 388-389,399 Scaling all correlations, SAC 359,374 Scanning calorimeters 113 Second Law 9,325,341,346 Second-order process 158 Second row 246
Second solvation shell 249 Second solvation sphere 248 Secondary electrons 260 Secondary reaction 295 Selective ejection 287, 289 Selective ion flow drift tubes, SIFT 305 Selectively excite 289 Self-chemical ionization 293
447
Self-consistent field, SCF 355,380,390-391 Self cooling 205 Semiadiabatic photocalorimeter 113-115 Semiempirical methods 355,374 Sequential addition of H2 244 Shape ofthe peak 238 Shapes of KERDs 238 Shock velocity 330-331,335 Shock temperature 330-33 I Shock tube 138,219,308,323,328,330,338
Single pulse 22,323-324,328,331-335,338-339,344,348, 350
Technique 324 Chemical 331
Shockwave 139,140,329 Silicon nitride 56 Sigma bond activation 235,239,244 Sigma donation 246 Single heating pulse 332 Single photon energy 277 Single reference theories 365 Slow equilibria 247 SN2 reactions 275 Solvated ions 276 Solvated protons 259 Solvation energies 266 Solvation enthalpy 6, 18, 131, 142, 146 Solvation entropy 6 Solvation equilibria 259 Solvation shell 241 Solvation sphere 241 Sol vent effects 161, 266 Solution transmitance 17 Spacing of vibrational energy levels 2 Spectroscopic properties 332 Spin change 219,245,248-249 Spin conserving 227 Spin-orbit coupling 389-390,399 Spin-orbit splitting 358,399 Spin-orbit corrections 358 Stacked pair 252 Static correlation 382 Stationary electron convention 20 Stationary points 272 Statistical mechanics 180 Step scan 218 Steric congestion 265,268 Steric effects 87 Stoichiometric chemical process 227
448
Stored wa vefonn inverse Fourier transform, SWIFT 287
Strain energy 417, 419 Stretching frequency 215 Sublimation enthalpy 203, 206
Of boron 353 Sublimation
Process 205 Temperature 211 Stan dard 211
Superconducting magnet 261,286 Supersonic expansion 238 Supporting electrolyte 154 Surface diffusion 205 Surface treatment 327 Switching potential 155 Symmetric reactions 275 Symmetry breaking 379 Synchrotron radiation 309
Pulsed 315 Syringe burette 80
T
T, diagnostic 363 Temperature-time curve 33,35 Temperature
(or heat flux) vs. quantity oftitrant added 23
vs. time or heat flux 3, 18, 22 rise, adiabatic 34-35
Thermal activity monitor, TAM 115, 121, 123, 128
Thermal distribution 306 Thermal electron convention 20 Thermal energy 308 Thermal equilibrium 291 Thermallensing 109, 138 Thermal power 112, 114, 118 Thermalized 238,291 Thermalization 284, 333 Thermochemical cycles 153,161-162,165,167,
170, 173 Third law method 15-16,325,346 Threshold appearance energy 267 Threshold energy 236, 277 Time-domain signal 287-288 Time of flight, TOF 307,312,315 Time resolution of PAC experiment 144 Titration calorimetry 23. 77-103 Total phase change enthalpy of the solid 178,
191-192,194-195 Total phase change entropy 193-195 Transducer 139 Transient infrared spectroscopy 215, 228 Transient species 221,236,328 Transition metal centers 235,239,244-245 Transition metal complexes 79
Transition state 271-272,275,317,348 Trapped ion 282 Trapping efficiency 284 Trapping electrodes 284-285 Trapping plates 286 Trapping voltages 286 Triflic acid 78,80-81,83,96 Triple point 183 Trouton's constant 206 Tungsten silicide 56 Tunneling 251
u Ultraviolet radiation 314 Uncertainty 31,363 Uncompensated solution resistence (iR drop)
157-158, 160 Unimolecular decay 338 Unimolecular decomposition 327,332-333,338 Unimolecular dissociation 262,277-279,303 Unimolecular loss 277 Unimolecular reactions 277,335,338 UV photolysis 215 tJV-Vis spectroscopy 9,15
v Valence shell 244 Vapour pressure 203-208 Van't Hoffplots 8,10,12,15-16,21 Very low pressure pyrolysis 24, 138 Vibrational frequencies 306-307,385 Vibrational states 310
w Wave function 375 Washburn corrections 34-36,41 Weakly bound species 277 Well depth 271,316,318 Working electrode 154-155, 157
x X-ray diffraction 98
z Zero energy 314 Zero kinetic energy 238 Zero-point energy, ZPE 317,357,362,385-386
