INDEX

ab initio methods 459, 464

absolute configuration 144, 158

absorption dissymmetry ratio 165

absorption spectroscopy, optical absorption

spectroscopy 112–116, 120, 124,

126–134

p-acceptor 18, 31

accuracy in calculations 484, 485, 490,

495–497

acetaldehyde 371

acetic acid 373

acid-base equilibrium 390, 391, 392,

394, 395

actinide ions 289

activation 367, 372, 375; energy 396,

402; parameters 385, 396–401,

413–416

activity 60, 61, 62

adiabatic cooling 97

adiabatic pathway 312

adiabaticity 241, 246

aggregation of molecules 58, 63

agostic interactions 476

alkali metal catalysis 343, 344

alkoxyl radical 381, 382

alkyl exchange 399

aminopolycarboxylate ligands 294, 296, 297

anion effect 394–395

anion-anion reactions 311, 347

anisotropic medium 203

anisotropy 62

anisotropy barrier 95

annealing 113, 115–120, 122–130,

133–134

antibonding (acceptor) molecular

orbital 20

antiferromagnetic order 63

antiferromagnetically coupled 46, 56, 59

antiferromagnetism 75

antitumor activity 304, 319

antitumor complexes 307, 308

aqueous cluster 300

p-arene-bpy compounds of Ru(II) 299

p-arene ligand 299

Arrhenius 396, 403, 406

asymmetry parameter of efg, h 41, 45

A-term 10–13

atoms in molecules (AIM) 473, 477

axial ZFS parameter, D 40, 41, 44, 47, 48,

49, 53

B-term 11–13

B3LYP 467, 482, 496

backbonding 472, 476

p-backbonding 1, 18, 30, 31

basis sets 468, 469

[Be(Cl)(12-crown-4]2þ ,[Be(H2O)(12-crown-4)]

2þ ,[Be(NH3)(12-crown-4)]

2þ 349

[Be(Cl)(crown ether)]2þ 291

Beer’s law 204, 207, 211

Bein, K. 144, 145

beta-scission 382

bidentate diamine ligands 167

Bigeleisen/Goeppert-Mayer

Formalism 429

Bijvoet method 190

bimolecular 372, 375, 377, 398, 399, 412

bimolecular reactions 486

biotransformation 307

biphotonic event 206

Bleaney-Bowers equation 78, 80

Physical Inorganic Chemistry: Principles, Methods, and Models Edited by Andreja BakacCopyright � 2010 by John Wiley & Sons, Inc.

501

Bloch wall 76

blocking temperature, tb 63

blue copper 2, 26, 27, 29–32

Bohr magneton 72

Boltzmann distribution 72, 82, 102

Boltzmann factor 45

bonding (donor) molecular orbital 20

bonding analysis 472, 473

Bonner Fisher model 91

boranes, chiral structures 164

Born cycle 241

Born-Druid-Nernst theory 343

boron compounds 236, 237

Brillouin function 14, 73, 101

bromide 373, 375

g-butyrolactone 350, 351

C/A Nomenclature 147, 148

Cahn-Ingold-Prelog (CIP) rules 146, 147,

149, 154

carbon radical 371, 415

carbonate complexes of Co(III) 255

carbonyl 372

carboplatin 305, 306

Car-Parrinello shell 291

CASPT2 467, 468

catalase 113, 114, 116, 119

catalysis 384

CCSD(T) 466, 467

CD component rule 168, 181, 184,

ceruloplasmin 116

charge

separation 232

transfer (CT) 1, 3, 4, 18–22, 237, 238,

262

transfer excited states 18–22

transfer transitions 167

chiral actinide complexes 164

chiral ligands 145

chloroperoxidase 116, 128, 133

circular

dichroism (CD) 1, 8–10, 152, 163,

165–177,

helicates 156

polarization 165, 175

circularly polarized luminescence

(CPL) 177

cis-dihydride rhodium(III) 341

cis-platin 304, 305

cis-trans isomerization 23460Co 112, 116, 124, 130

Co-C bond 255

Co(NH3)5X2þ (X ¼ Cl, Br, NO2, N3)

253 – 255

Co(bpy)33þ 225

Co(CN)63� 231

Co(CO)3NO 260

Co(NH3)63þ 231, 257, 258

CO3H radical 255

cobalamin 116, 303, 304

aqua 303, 340

cyano 303

5-deoxy-adenosyl 303

cobalt 116, 125, 127

coercitive field 76

competition kinetics 381

competitive fractionation 428

complete active space self-consistent field

(CASSCF) 466, 468

complex refractive index 203

composite parameters 396

Compound 0 114, 127–128, 132–133;

See also peroxo-ferric

Compound I 119, 122,123, 127–129, 132

Compound II 119, 128–130, 132

Compound III 128, 132; See also

oxo-ferrous, superoxo-ferric

Compound Q 59

compressibility coefficient of

activation 274

computational resources 468, 490

concerted 396–397

configuration interaction (CI) 5, 20

configurational CD 172

configurational symmetry 148

conformers and sampling 495

consecutive reactions 382–384

cooperative phenomena 76

copper 59, 60, 61, 62, 63

copper proteins 116, 117, 134

core excited states 22–34

corpuscular nature of light 200

corrin ring 303

coupled-cluster theory 466

covalency 1, 6, 21, 25, 29, 30, 32, 33, 34

covalent delocalization 26

trans-[Cr([14]aneN4)(CNRu(NH3)5)2]5þ

261

502 INDEX

Cr(bpy)33þ 217–221

Cr(phen)33þ 241

CrIII(NH3)5Xzþ (X¼H2O, Cl, Br, I, SCN)

239

cryoradiolytic reduction 112–116, 119,

120, 124, 130, 134

cryosolvents 110, 112, 115, 117, 127, 128,

133137Cs 118

C-term 10–14

CTTS 234

Cu K-edge 25

Cu(I) 24, 25

Cu(II) 2, 3, 5–7, 9, 13, 14, 18–20, 22, 25,

29, 32

CuCl4 19, 22, 25–27, 29

Curie law 53, 72, 92

Curie temperature 76

Curie-Weiss law 75, 92, 99

cyclic voltammetry 285, 344, 345

cyclization 381, 398

CYP101 120–124, 129, 130, 132–134

CYP119 124

cytochrome b5 116, 130

cytochrome c 113–116, 119, 130, 134, 312,

313, 314, 315

cytochrome c oxidase 114, 116

cytochrome c peroxidase 130

cytochrome c552 120

cytochrome P450 114–115, 120–122, 124,

129, 130, 133, 138, 140, 142, 327, 332,

337, 339, 341, 3454

D2 symmetry 152

D3 symmetry 148, 153, 176

dead-end intermediate 412

Debye temperature 84

Debye-H€uckel 312, 343

Debye-Waller factor 43

Delepine’s active racemate method 181

densitometer 287

density functional theory (DFT) 3, 50, 51,

57, 58, 432–437, 292, 293, 307, 341,

346, 348, 459, 464, 467, 468, 469, 473,

475, 477, 496

detector response 220

deuterium 371, 401, 403, 413

Dexter treatment of energy transfer 232

diamagnetism 70

diastereomer solubility criterion 180

differential orbital covalency (DOC) 30

diffusion-controlled 302, 325, 327, 335,

338

dihydrogen bonding 475

diiron center 117,118

diiron(III) 46, 51, 53, 59, 60, 61, 62

diiron(IV) 44, 51, 53, 54, 59

dilatometer 287

dioxygen 114, 118, 120, 121, 125, 126, 128,

133; O-O bond 120, 121, 124, 125,

128, 133

dioxygen reduction 425, 426, 444–448

disproportionation 389, 392, 409, 410

dissociation 369, 372, 375, 376, 385,

394

distorted square planar structures 154

dithionite 375

dodecyl b-d-maltoside 63

s-donor 18, 31

p-donor 1, 18, 30, 31

Doppler shift 42

dose dependent yield 115, 116–117, 122,

124, 131–133

double-pump flash photolysis 225

10Dq 5–7, 27

dynodes 217

effective core potential (ECP) 469

effective nuclear charge (Zeff) 19, 25

Eigen-Tamm-Wilkinsmechanism 281, 302

electric dipole transition 4, 8, 9, 13, 18, 20,

25, 26–29, 32

electric field gradient, efg 41, 44, 45

electric quadruple transition 25

electromagnetic waves 200

electron correlation 464, 466, 467, 469

electron ionization mass spectroscopy 58

electron microscopy 109, 112, 131

electron paramagnetic resonance (EPR)

9, 10, 16–18, 26, 32, 85

electron transfer 241, 259, 397, 398,

438

electron–electron repulsion 5, 6, 21, 27, 30,

32

electronic absorption spectroscopy 3, 8

electronic g tensor 42

electronic Hamiltonian, he 40, 41, 48

electronic paramagnetic resonance, see EPR

INDEX 503

electronic structure 1–34

electronic structure methods 463

electronic Zeeman interaction 40, 41

electrons, radiolytic 109–112, 116, 125,

131, 133, 134

electrostatic effects 5, 34

electrostriction 297, 319, 320, 323

elementary reaction 369

elimination 372, 410, 415; beta 371, 381;

reductive 373, 406, 407

emission-detected CD 176

energy decomposition analysis 473

enthalpy 396, 411

entropy 367, 411

enzyme active sites 491

enzyme kinetics 367

epr spectroscopy 40, 41, 53, 55, 59, 62, 63,

113–131, 135

equilibrium isotope effect 431–437

equilibrium kinetics 385, 386

EXAFS 58, 114, 131, 134, 293, 300

exchange correlation functional 467

exchange coupling 40, 42, 77

exchange energy 75

exchange mechanism of energy

transfer 233

excimer 231

exciplex 231

excited state annihilation reaction 232

excited states 468, 478

excited states of representative elements

(np*, ns*, pp*) 234

excited-state radiative decay 226

exciton CD 158, 173–175

expectation value of electronic spin, hsi 41,

42, 43, 44, 45, 46, 47, 48, 49, 53, 54, 57

exponential 377

extended x-ray absorption fine structure

(EXAFS) 1, 23–25

extinction coefficient 4

Eyring equation 396, 403, 463

57Fe 3957Fe M€ossbauer spectroscopy 39, 40, 55,

60, 61, 62

Fe(II) 16, 17, 21

Fe(III) 3, 5, 6, 14, 15, 18, 21, 22, 27, 28,

30–33

FeII 43, 44, 46, 47, 63

FeIII 41, 56

FeIV 41, 43, 46, 47, 48, 49, 50, 51, 54, 56,

57, 58, 59

FeIV¼O 47, 50, 51, 53, 55

FeV 51, 53, 55, 56, 57, 58

FeV¼O 55

FeIV-FeIII dimer 53

Fe(H2O)62þ 241

Fe(H2O)63þ 241

femtosecond - nanosecond time domain flash

photolysis 223

Fenton 47, 50, 413–415

Fermi’s golden rule 228, 232

ferredoxin 119

ferric phosphate 63

ferrimagnetism 77, 95

ferromagnetically coupled 51, 54

ferromagnetism 75

ferrozine 298, 315, 317

Fe-S clusters 46, 59, 60, 61, 62, 63

final states 21, 27, 28, 30, 32, 33

first law of photochemistry 199

first-order kinetics 369–372

Flack parameter 190

flash photolysis 214–225, 281, 324, 332,

339

flow (continuous) 280

flow methods 280

F€oster treatment of energy transfer 233

Frank-Condon reorganization energy 242

free energy 367, 372, 396

linear relationship 403, 420

front-face irradiation 215

frozen solution 39, 42, 45

gadolinium(III) 290

GdIII 295

geminate recombination 250

geometric structure 1, 3, 24

glass transition 112, 113

glass-forming solvent 58

ground state 3, 16, 17, 38, 206

gyromagnetic factor 71

half-order kinetics 375–376

Hamiltonian operator 464

Hamiltonian, 39, 40, 54

Hammett 420

Hartree-Fock level 348

504 INDEX

Hartree-Fock method 464, 465, 467, 469,

475

HeisenbergHamiltonian 78, 80, 92, 99, 104

helical chirality 149

heme 30, 31

heme iron 113, 123, 128, 130

heme oxygenase 119–122, 126–129

heme protein 111–115, 119–121,

122–133

hemoglobin 115, 119–122, 125–126, 130

heterolytic cleavage 369, 371

high pressure electrochemical cell 345

high spin-low spin transitions 94

high-spin 41, 44, 47, 324, 327, 331, 332,

335, 338, 339

high-spin FeII 44

high-spin FeIII 41, 43, 45, 46, 47, 48, 49, 50,

59, 63

high-temperature series expansion 75, 91

Hilbert space 93

homolytic cleavage 369, 398, 399, 415

Hund’s rule 81

Hush 310, 311, 313, 315, 319

hydrogen

abstraction 234

atom 372, 394, 404, 413, 417

bond 401, 408

peroxide 450–452

hydrogenase 59

hydrogenation 481–485

hydroperoxo 368, 371, 372, 374, 375, 384,

394, 405

hydroperoxo-ferric intermediate, see Peroxo-

ferric, Compound 0

hydroxo-bridged complexes 117, 118

hyperconjugation 401

hyperfine coupling 26, 30, 32

hyperfine interaction 41, 86, 89

impurities 82, 88

initial rate 388

inner filter in photolysis 210

inner-sphere 397, 398

integer spin 44, 50, 53

p-interaction 1, 7, 17–20, 22, 31

intermediates

reactive 110, 127, 129–132, 134

catalytically active 119, 122, 123,

127–129

in X-ray crystallography 131–134

mixed valent 117

intermolecular coupling 70

internal magnetic field, bint 41, 42, 43, 44,

45, 46, 49, 54, 57, 60

intersystem crossing 489

intramolecular 372, 373, 38

intramolecular coupling 70

ion-pairing 390

IPCT 257

iron 40, 41, 44, 59, 61

iron–sulfur 32–34

iron-sulfur cluster 46, 59, 60, 61, 62, 63,

119, 132, 134

irradiation, 110–111, 115, 122

irradiation dose 112, 122, 128, 131, 132

g-irradiation 113, 116–119, 124, 126–127

Ising model 89, 90

isoelectronic 300

isomer shift, d 40, 62

isotopic labelling 289, 291

isotopic substitution 269, 343

IUPAC nomenclature rules 146, 148

Jahn–Teller distortion 7, 19, 21

Ka 385, 393, 394, 409, 410

Kagom�e lattice 98

Keplerate structures 98

kinetic isotope effect 401–411, 437–445

kinetic probe 380–381

King, V. L. 143

Kohn-Sham orbitals 467

Kotani theory 74

Kramers ion 15–16

Kramers systems 43, 44, 48

Kuhn anisotropy factor 9

Kuhn, W., 144 145

labeling 401, 406

lanthanide ions 270, 285, 289, 299

lanthanide shift reagents 299

lanthanides 299

Laporte forbidden transition 4, 8

Larmor precession 44

laser 385, 386, 412

laser flash photolysis 321, 327, 335, 337

LAXS 293

least squares 370, 391

INDEX 505

Lenz rule 71

LIESST 95

ligand centered (LC) 238, 262

ligand donor strength 21

ligand field (LF) 238–240

excited states 3–18

splitting 5–7, 17, 27, 30, 32

theory (LFT) 3–10

ligand K-edge 31–34

ligand K-pre-edge 31–33

ligand to metal charge transfer

(LMCT), 18–21, 237, 238, 244, 245,

247–250, 253, 255–257

ligand valance ionization energy 19

ligand–metal bond 1, 19, 32

light intensity 199, 203 – 211.

light waves 200

limiting reagent 376

linewidth, G 40

linkage isomerization 234

long-wave approximation 4, 25

low-spin 326, 335, 338

luminescence dissymmetry ratio 177

M(pc)X (M¼Rh(III), Al(III) ; X¼Cl, Br)

225, 226

magnetic

anisotropy 63

circular dichroism (MCD) 1, 10–18,

113, 114

dipole 4, 9–10

dipole interaction 41, 42, 43

entropy 85

excitation spectrum 70, 82

field strength 71

flux density 71

hyperfine interaction 40, 44, 46, 47, 57,

58, 62, 63

hyperfine splitting 42, 62

hyperfine tensor, a 42, 44, 47, 40, 50,

53, 54

induction 71

level crossing 78, 101

moment 41, 42, 71

resonance imaging (MRI) 290,

299

susceptibility 41, 71, 102

magnetically ordered

compound 63

magnetization 71

curves 44, 45, 49

hysteresis 76, 97

manganese 119, 131, 134

many-electron states 21

Marcus theory 310, 311, 313, 315, 319

Marcus-Hush 246

Mars mission, NASA 39

matrix isolation 110, 111, 113, 134, 135

(ref 11)

Maxwell thermodynamic equality 288

metal

carbonyls 474

centered (MC) 238

K-edge 24–28

K-pre-edge 27

L-edges 28–31

valence ionization energy 19

metal-to-ligand-charge-transfer

(MLCT) 1, 18, 222, 226, 238,

244 – 246, 258–260

metallocenes 149

metalloenzymes 445–451

metalloproteins 459

metamagnet 77

methane 59

methane monooxygenase, MMO 46, 59,

60, 62, 117, 118

methanol 59

methemerythrin 117

methemoglobin 323

methyl radical 382

methylaquocobaloxime 255

methylviologen (MV2þ ) 222

metmyoglobin 321, 335

microscopic reversibility 368, 417

MII(bpy)32þ (M ¼ Ru, Os) 259

mitochondria 62

mixed-valent dimer 53

MM’CT 261

Mo72Fe30 cluster 300, 301 (see also

aqueous cluster 300)

model construction 491

molecular

dynamics (MD) 462, 487

molecular field model 76

molecular magnetism 69

molecular mechanics 459, 460, 464,

494

506 INDEX

molecular orbital 19–21, 29, 32, 465, 472,

475, 476, 477

molecular orbital theory 21

molecular properties 459, 472, 473, 478

molecular structure 472, 474, 483

Møller-Plesset perturbation theory 466

Monte Carlo simulation 93, 99

M€ossbauer spectroscopy 88, 95, 114–116,

118–120, 126

multiconfiguration self-consistent field

(MCSCF) 466

multiple scattering theory 23

multipole expansion 4, 25

multireference configuration interaction

(MRCI) 467, 468

multireference methods 466

multistep volume profile 308, 310

myoglobin 59, 113, 115, 120–122,

125–130, 132, 133

nanoparticles 62, 63

naphthalene dioxygenase 134

NASA mission 39

natural bonding orbital (NBO) analysis

473

near-edge region 23

Ne�el temperature 63, 76

nephelauxetic effect 6

neutron scattering 85, 101, 103

nickel 117

nitrite 392, 412

nitrite reductase 134

nitrogen donor-based complexes 50, 51

nitrogenase 43, 119

nitrone 415, 418, 419

nitroxyl 415, 417

L,D nomenclature 149

NO2 radical 256

non-Kramers ion 16–18

non-Kramers systems 44

nuclear

Hamiltonian, hn 41

magnetic moment, mn 42, 43

precession frequency 44

octahedral structures (OC-6) 147,

150–153

ONIOM method 493

O-O Raman mode 124, 127

optical electronegativity 245

rotation 143, 144, 164

dense condition 210

dilute condition 210

orbital angular momentum operator 9, 10

orbital moment 71

organometallic chemistry 269, 276

organometallic species 286, 298

oscillator strength 4

outer-sphere

complex 302

mechanism - 310, 311, 317

p-overlap 18, 20, 21

s-overlap 20, 21

oxaliplatin 305, 306

oxidation state 39, 41, 57, 60

oxidative addition 478

oxo group 51, 56, 57

oxo-bridged 51, 55, 59, 118

oxo-ferryl intermediate 122, 126, 130, 132;

See also Compound I, Compound II

oxo-ferrous, superoxo-ferric 114, 116, 120,

122–124, 126, 128, 129, 132, 133

oxygen 372, 382, 384, 411, 414

32P 111, 124

P450cam, see CYP101

parallel

path 380, 395;

reactions 377–382

paramagnetic 13, 18

complexes 40, 45

paramagnetism 70

parity forbidden transition 4, 8

partial molar volume 274

partial spin pairing 81

partition functions 429, 430, 436

Pascal’s constants 71

peroxidase 114, 116, 119–121, 128–130,

133, 134

peroxo 51, 53, 59

peroxo-cobaltic 127

peroxo-ferric 114, 119–129, 132–133

peroxyl radical 380, 419

perturbation theory 172

Pfeiffer-effect 175, 176

pH effect 390–394

phenothiazines 317

photocathode 216

INDEX 507

photochemical reactor 210

photodiode 216

photodiode array 216

photodissociation 234

photoelectron spectroscopy (PES) 24

photoisomerization 234

photolysis 412, 416

photomultiplier 216–222

photon’s kinetic momentum 205

photoreduction 132–134

Photosystem II 131, 134

phthalocyanine (pc) 225, 226

pill box 279, 280, 288

piston cylinder (high pressure)

apparatus 278, 280

planar chirality 149

plastocyanin 2, 26, 27, 29, 31, 32

pMMO 59, 60, 61, 62, 63

polarizable continuum methods

(PCM) 470, 471

polarization functions 469

polarized absorption 22

polarized light 202, 225

polyaminocarboxylate complexes

183–188

polyatomic anions photochemistry 236

polynuclear system 42

porphyrin 321, 324, 329, 331, 337, 340, 341

potential energy 367

potential energy surfaces 460, 463, 464,

481, 487

powder average 42, 43

pre-edge 1, 22, 24–29, 31–34

pressure-jump method 281,

primary photochemical processes 199

product ratio 378

protein 59

pseudo A-term 12, 13

pseudo nth order 376–377

pseudo-first order 373–377

Pt0(PPh3)2C2H4 260

pulse radiolysis 283, 380

pump and probe 215

putidaredoxin 131

pyridine-2-azo-p-diethylaniline 303

QM/MM methods 493

quadrupole

doublet 41, 44, 45, 51, 57, 60, 62, 63

interaction 40, 41

splitting, Deq 41, 42, 45, 46, 47, 50, 53,

57, 59, 60, 61, 62, 63

quantum

mechanics of nuclei 488

Monte Carlo simulation 93

tunneling 95

yield 199, 239

R/S nomenclature 146

Racah parameter 6

racemic mixtures 146, 161

racemic structures 151

racemization 146

radiation

chemistry 109, 114, 131, 134, 135,

136

damage 109, 131, 132

dose 112, 115, 116–118, 122, 126, 128,

130–133

radiationless relaxation rate constant

228 – 231

radiative decay rate constant 226

radical 56, 109–111, 116–118, 122, 131,

133, 135

clock 381

self-reaction 373, 375, 412

anion 373, 375

radical-ion pair 250 – 253

radioactive isotopes 111, 124

radiolysis 109–116, 118, 120–122,

124–132, 134

radiolytic reduction 110–112, 114–117,

119–122, 124, 126, 128, 130–134

Raman spectroscopy 115, 120, 124, 126,

127, 133

randomly oriented molecules 42, 45

rapid freeze quenching 47, 49, 50, 58

rate constants 460, 481

rate law 367–389

rate-limiting 372, 375, 387, 410, 417, 483

reaction coordinate 367, 368, 402, 407

reaction mechanisms 460, 479–481

reactive intermediates 459, 460

recoilless fraction, f 43

Redlich-Teller product rule 430

reduction potential 387

reductive coupling 410, 411

reductive elimination 372, 406, 407

508 INDEX

ReI(CO)3(1,10-phen)Cl 259, 260

ReI(CO)3(2,20-bpy)X (X¼ Cl, Br) 222,

259

ReI(CO)3(4-phenylpyridine)2Cl 226

relativistic effects 469

relaxation, after annealing 111–113, 115,

117, 119, 120, 123

relaxivity 300, 348

remnant magnetization 76

resolution 40

resonance Raman (rR) 22

Rh(NH3)63þ 231, 239

Rh(phen)33þ 241

rhombicity, E 40, 44, 47, 48, 49, 53

ribonucleotide reductase 46, 117, 118

Richardson, F. S. 143

ring conformation 149

ring-pairing method 149

rotational strength 8–9, 168

rotatory strength 165

[Ru(edta)(H2O)]� 327, 331, 332

rubredoxin 116

S ¼ 0 41, 42, 45, 46, 54, 60, 63

S ¼ 1/2 41, 44, 45, 53, 56, 58

S ¼ 1 50, 54

S ¼ 2 43, 44, 45, 48, 50, 53, 54

S ¼ 3/2 53

S ¼ 5/2 43, 44, 48, 49

S K-edge 32, 33

Saito, Y. 143

sample and hold circuitry 219, 220

saturation magnetization 14–18, 73, 78, 82

scavenger 116, 133, 388, 399, 417

Schottky anomaly 85

Schr€odinger equation 464, 465, 468

second law of photochemistry 199

secondary photolysis 211

second-order kinetics 372–375

sector rules 168

see-saw structures (SS-4) 147

selectivity 483

s-electron density 41

selenium, chiral structures 163

semiempirical methods 464, 467, 474

side-on 372

side-on irradiation 215

single-molecule magnets 95

skew-line convention 145, 148, 161

SMCT 257

sMMO 59, 60, 62, 63

sodium nitroprusside 42

solvated electron 234

solvent

cage 250

effects 470, 480, 481

isotope substitution 271

molecules: explicit treatment 471

(solvento)Ru(II) species 298

Soret (region) 321, 322, 326

specific heat capacity 84

spin

chain 90

change 322, 327

crossover 489

density 325

dipolar interaction 58

expectation value 16, 17

frustration 97

Hamiltonian 1, 15, 17, 19, 39, 40, 50

moment 71

multiplicity 228, 335

Peierls transition 92

quantum number 70, 77, 100

relaxation 43, 44, 45, 47, 49, 50, 53

reorganization 327

state 312, 324, 332

trap 419

spin-admixed 324, 325, 331

spin-allowed transition 4, 7, 9

spin-coupled system 46

spin-forbidden reactions 489

spin-only magnetism 73

spin–orbit coupling (SOC) 12, 13, 29, 30,

70, 74, 86, 95, 228, 230

spin–orbit parameters 13

spin-pairing energy 6

spin-phase transitions 97

spin-spin interaction 75

spin-state change 325, 338

square antiprism structures 161

square-prismatic structures (SPY-5 and

SPY-4) 147, 154, 155

SQUID 83, 84

statistical mechanics 463, 471, 495

steady-state 386–388, 416

Stokes shift 229

Stoner-Wohlfarth model 76

INDEX 509

stopped-flow 47, 280, 281, 302, 327, 332,

335, 337, 340, 343, 384

strong coupling limit 229

substituent effects 460, 478, 481

sulfur, chiral structures 163

sum rule 13

superoxide 448–449

superoxide dismutase 116, 344

superoxo-ferrous complex 125

superparamagnetic relaxation 63

superparamagnetism 76

supramolecular complexes 155

Swift and Connick 346

synchrotron 22–23

TAML activator 55, 56, 57

TAML activator B* 55, 56, 57, 58, 59

TAML activator DMOB 56, 57

TAML activator MAC* 57

Tanabe–Sugano diagram 5, 6

tellurium, chiral structures 163

temperature 385, 396, 398, 403, 406, 411,

416

temperature-independent

paramagnetism 74, 75

temperature-jump (method) 281, 302,

303

tetrahedral (T-4) structures 146, 147,

153–154

tetranuclear complexes 156

time-dependent DFT (TDDFT) 168, 169,

174, 468, 478

total energy 465

TPA ligand 51, 52, 53, 54, 55

trans effect 305

transfer of electronic energy 232, 233

transition moment 3, 4, 13, 18, 20, 21

transition state 367–389, 460, 462, 476,

478, 482

transition state theory 460, 463, 481,

485

trans-labilization 299

trans-Pt-N bond 308

trapping reaction 327, 331, 332

trigonal tricapped prism 159

trigonal-bipyramidal (TBY-5) 147, 154

trigonal-pyramidal (TPY-3) 147

triple helicate structures 157

12-tungstoaluminate (5�/6�) couple 343

tunneling 403, 406, 487, 489

two-window high pressure cell 279

ultrasound method 281

unimolecular reactions 369, 381, 396, 398,

486

UV/Vis spectroscopy 47

Van Vleck equation 72, 74, 78

variable-temperature variable-field MCD

(VTVH MCD) 14–18

vibrating sample magnetometer 84

vibrational CD (VCD) 177

vibrational frequencies 463, 478

viscosity 276, 285

vitamin B12 340, 341

volume of activation 274–276

water oxidation 426

wavefunction 464, 466, 468

weak coupling limit 230

Weiss district 76

Weiss temperature 75, 76, 104

Werner, A. 143, 153, 164, 180

whole cells 61, 62, 63

WMOSS software 40

X.(X ¼ Cl, Br, I, SCN, O) 234–236

X2.� (X ¼ Cl, Br, I, SCN) 234, 235

XANES 115, 134

XAS 134

x-ray absorption spectroscopy (XAS) 1,

22–34

X-ray crystallography 109, 112, 131, 132,

133

X-ray diffraction 145, 163, 190,

X-ray irradiation 119, 125, 128, 131–133

X-ray spectroscopy 109, 114 - See also

EXAFS, XANES, XAS

XY model 90

yield of radiolytic electrons 110–112, 133

Zeeman effect 10, 11, 14, 15, 17, 71, 85, 95

zero-field splitting (zfs) 12, 14, 15–17, 40,

41, 42, 43, 44, 45, 53, 70, 81, 86, 87, 95

zero-order 392, 400

zero-point energy 401–403, 411, 488

zinc 60, 62

510 INDEX