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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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ADVANCES IN CHEMISTRY SERIES
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Photochemistry and Radiation Chemistry Complementary Methods for the Study of Electron Transfer
James F. Wishart, EDITOR Brookhaven National Laboratory Daniel G. Nocera, EDITOR Massachusetts Institute of Technology
American Chemical Society, Washington, DC
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
12 Photoinduced Electron and Proton Transfer in a Molecular Triad
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SuChun Hung, Alisdair N. Macpherson, Su Lin, Paul A. Liddell, Gilbert R. Seely, Ana L. Moore, Thomas A. Moore*, and Devens Gust Department of Chemistry and Biochemistry, Center for the Study of Early Events in Photosynthesis, Arizona State University, Tempe, AZ 852871604
A series of molecular triads, consisting of a porphyrin (P) covalently linked to a carotenoid polyene (C) and a naphthoquinone moiety (Q), have been prepared. Triad 1 features a quinone with an internally hydrogen-bonded carboxylic acid group. The photochemical properties of these molecules have been studied using steady-state and transient absorption and emission spectroscopies in three solvents: benzonitrile, dichloromethane, and chloroform. Each of the triads undergoes photoinduced electron transfer from the C1PQ singlet state to yield the charge-separated state C-P. -Q.-. An electron transfer reaction from C to yield C .+ -P-Q.- competes with fast electron-hole recombination in C-P.+-Q.-. Triad 1 produces the final C . + - P - Q . - state with the 0.22), a factor of ca. 2 higher highest quantum yield of the series than for reference triads. Following the initial photoinduced electron transfer, a fast (k ~ 10 s-1) proton shift from the carboxylic acid to Q.- generates the semiquinone, increasing the lifetime of P.+ and the yield of electron donation by C. In model P-Q dyads, the species P.+ is shown to be longer livedfor quinones thatfeature an internal hydrogen bond. A thermodynamic model is proposed in which the increase in the lifetime of the P.+ moiety by the proton shift is attributed to the pK of the Q/Q.- couple, which dramatically lowers the driving force for electron-hole recombination. +
12
Natural photosynthetic reaction centers, which are responsible for the conver sion of light energy into chemical energy in photosynthetic organisms, employ a multistep electron transfer strategy to achieve charge separation across mem branes with a total quantum yield near unity. Thus, at each intermediate step * Corresponding author. ©1998 American Chemical Society
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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15
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Studies of Superoxide with Manganese Complexes and Manganese Superoxide Dismutase from Escherichia coli Diane Esther Cabelli Chemistry Department, Brookhaven National Laboratory, Upton, NY 119735000
II
11
The reactions of TTHA (Mn -triethylenetetraminehexaacetate) complexes with HO -O - radicals were studied (pH 2.5-9.5), and a mechanism was suggested that involves the formation of a transient Mn -) complex. At low pH, this complex is protonated, with the release of H O . At higher pH, the dismutation of O - from the Mn TTHA + O -) is comequilibrium complex (Mn TTHA(O -)3petitive with protonation. At low pH, the results indicate that there is a rapid first-order process that may be an isomerization from end-bound to side-bound of the attached superoxide radical. In contrast, the kinetics of the dismutation of superoxide radical by Escherichia coli MnSOD (manganese superoxide dismutase) were measured and shown to fit a mechanism involving the rapid reduction of Mn SOD by superoxide followed by both the direct reoxidation of Mn SOD by superoxide and the formation of a Mn SOD(O -) complex. The differences in the mechanisms are discussed. 2
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The reactions of superoxide radicals with metal complexes have received much attention as 0 ~ can play a role in cycling oxidation states in metal complexes ( J ). This feature has been implicated in catalytic processes such as the Fenton type chemistry (M + H 0 — M + HO + OH"; M + 0 M + 0 ), which is thought to be involved in hydroxylation processes (2). Reactions involving 0 ~ radicals have also been tied to the deleterious effects of oxygen upon aerobic organisms (1,3), probably as a result of similar Fenton type chemical reactions. Superoxide dismutases (SODs) are thought to have evolved as nature's 2
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Nonadiabatic
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
20
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ch020
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ch021
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ch021
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ix001
Author Index Belloni, J., 293 Bobrowski, K., 131 Brigham, Elaine S., 359 Brunschwig, Bruce S., 279 Cabelli, Diane Esther, 247 Chang, F. K., 111 Closs, G., 161 Craw, J. S., 263 Creutz, Carol, 231 Durham, B., 99 English, A.M., 81 Farver, 0., 65 Fenwick, C. W., 81 Fox, T., 81 Fujita, Etsuko, 279 Gauduel, Y., 331 Gelabert, H., 331 Geren, L., 99 Gray, Harry B., 51 Green, N., 161 Gust, Devens, 177 Hazzard, J. T., 81 Holeman, J., 131 Hung, Su-Chun, 177 Hush, N. S., 263 Johnson, M., 161 Johnson, Stacy A., 359 Keller, Steven W., 359 Khatouri, J., 293 Liddell, Paul A., 177 Lin, Su, 177 Macpherson, Alisdair N., 177 Mallouk, Thomas E., 359 McLendon, George L., 145
Miller, J. R., 161 Millett, F., 99 Mines, Gary A., 51 Moore, AnaL., 177 Moore, Thomas A., 177 Mori, Yukie, 279 Mostafavi, M., 293 Mutz, Mitchell W., 145 Onuchie, J. N., 111 Pecht, 1., 65 Penfield, K., 161 Pielak, G. J., 99 Piotrowiak, Piotr, 219 Poznanski, J., 131 Ramirez, Benjamin E., 51 Regan, J. J., Ill Reimers, J. R., 263 Richter, Helen Wilkinson, 5 Saunders, A. J., 99 Saupe, Geoffrey B., 359 Schwarz, Harold A., 231, 279 Seely, Gilbert R., 177 Sutin, Norman, 231 Szalda, David J., 279 Tollin, G., 81 Tsaprailis, G., 81 van Eldik, Rudi, 315 Wang, K., 99 Wierzchowski, K. L., 131 Winkler, Jay R., 51 Wishart, James F., 1, 35, 81, 145 Wright, J. L., 99 Yonemoto, Edward H., 359 Zeng, J., 263
381
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
Subject Index
Downloaded by 95.157.17.76 on October 20, 2009 | http://pubs.acs.org Publication Date: April 17, 1998 | doi: 10.1021/ba-1998-0254.ix002
A
a helices, electronic coupling, 56 3d -+ 4s Absorption, Fe2+(H10k complex, 273-274 Accelerators development, 2 pulse radiolysis, 174 radiation safety, 39-41 study of radiation chemistry, 35-SO Acetylenic derivatives, Ni-catalyzed C02 insertion, 280 Actinometers, photochemical experiments, 12 Adducts hydroxyl radical, 22 metal ions, 18-19 Adiabatic theory, ET kinetics in solutions, 334 Adsorption reactions, turnover rate constant, 302 Aerobic organisms, reactions involving 0 1radicals, 247-248 Alpha particles, pulse radiolysis, 47-48 Alternative pathways, renormalization, 114, liS/ Amine nitrogen in macrocyclic complex, three potential isomers, 24lf Amino acids, proline-bridged aromatic, 131-143 p-Aminonitroterphenyl (p-ANTP) ions associated with photoinduced charge-separated species, 224-229 ion-size dependence of triplet absorption band,22S-227 rate vs. temperature dependence, 228/ spectral shifts vs. radius of salt anion, 227/ transient triplet absorption spectra in THF, 225/, 226/ Anchoring process, agglomeration, 367 Aqueous bipyridine, unique thermodynamic data, 242-243 Aqueous Fe1+(H20)6, spectrum for photodetachment of electron, 271/
Arg, reactivity of peroxidases with H10 1, 82 Aromatic species, ipso adduct, 22 Ascorbate oxidase catalytic cycle, 74 internal electron flow, 74 intramolecular and internal ET rate, 7577 reduction by col- radicals, 76/ reoxidation, 77 Association process salt concentration, 227-228 temperature dependence vs. activation energy, 228-229 Azide radical, reactions, 29-30 Azurin bimolecular electron tunneling reactions, 120-128 copper, ligands, and Ru-(bpy)z(im)· (histidine) groups, 121/ coupling along ~}-strands in Ru-modified derivatives, 56 ET rates for D-A pairs, SI model system for intramolecular ET, 6773 pathway tubes for tunneling coupling from Cu to Ru(bpy)1(im), 122/ ribbon structure of Pseudomonas aeruginosa, 51/
B
1}-sheet, ability of hydrogen bonds to mediateD-A interaction, SS 1}-sheet proteins, ET rates for D-A pairs, S I Bacteria, azurins in energy-conversion systems, 67-73 Bacterial photosynthetic reaction centers, crystal structures, 360 Bifunctional redox proteins ET kinetics ofmaquettes, 145-159 stable triple helix maquette, I 58 Bimolecular ET reactions, uncertainties, 84
382 In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
383
Biological redox processes, pulse radiolysis, 66-67 Bipyridine-modified peptides, redox-active viologen at C-terminus, 147 Bipyridine-peptide-viologen complexes, structures and amino acid sequences, 147/ Bleaching end-of-pulse, 298 ground-state and excited absorption spectra, 236 Blue copper oxidases, one-electron oxidation of substrates to 0 2, 74 Blue copper proteins, ligand-to-metal charge-transfer interactions, 125 Blue shift, linear dependence on salt concentration, 227-228 Braking radiation, pulsed or continuousbeam generation, 38 Branching, short-lived electron photodetachment pathways, 347 Bremsstrahlung, pulsed or continuous-beam generation, 38 Bridge entrances, azurin, 123
Ceruloplasmin electron-uptake mechanism, 73 electron-uptake site, 74 Charge separation, photochemically induced, 359--379 Charge separation across membranes, multistep ET strategy, 177-178 Charge shift reactions, free-energy change, 168-169 Charge transfer to solvent (CTTS) transition aqueous ferrous ion, 265 definition, 265 Fe and Ru complexes, 266 stabilization, 33 Charge-recombination reactions, hydrogen bonding in P-sheets and a-helices, 57 Charge-separated states, fluorescence lifetimes and decay times, 1901 Chemical reactivity mechanisms, photochemistry and radiolysis, 3 Cleavage rate constant, hydrated pairs, 340 Cluster properties, nuclearity, 293 Cluster redox potential, determination by kinetics methods, 295/
co
photochemical formation with [Ni(2,2 ·bipyridine)3](C104) 2, 2821 yield and irradiation time on photolysis, 283/ yield from photochemical reaction of [Ni(2,2' -bipyridine)3](CI04) 2, 284t
c Cab-0-Sil ET across inorganic sheet, 373, 374f transient diffuse reflectance decays, 375/ transmission electron micrographs, 369/ UV-visible diffuse reflectance spectra, 370/ Cab-0-Sil diad composites, 370-375 lifetime and steady-state emission intensity data, 372/ transient absorption spectra, 372/ Carbon dioxide, reduction potentials, 232, 233/ Carbon dioxide complexes, tetraazamacrocyclic cobalt complexes, 240-2421 Carbon dioxide radical anion, reactions, 25-26 Carboxylation reaction, electrocatalytic, 280 p-Carotene, preparation, 182 Catalyst, ET process, 232 Catalytic ET mechanism, 31 Of semiquinone, 302-303 Catalytic relay, metal cluster, 308-310
C02
·
photochemical reaction with Ni(2,2 ·bipyridine)32+-TEA system, 290 photochemical reduction, 281-284 photoreduction with Ni(2,2 ·bipyridine)n2+ complexes, 279--292 C02 copolymerization, Ni(COD)2 as catalyst, 280 Coalescence progressive nuclearity, 293 silver clusters, 299 Co"LP 10V, effects of solution conditions, 1541 Co11LP 1rV bundle, molar ellipticity vs. temperature, 156/ com_p••v maquette circular dichroism spectra, 149/ UV-visible spectra, 152/ eom-Pn-V systems, rate constants, 1531 Cobalt, complexed with bipyridine ligands, 147
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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384
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
Cobalt complexes intermolecular and intramolecular ET reactions, 322-328 rate and activation parameters for ET reaction, 3261 redox reactions, 325 volume changes, 327 Cobalt-modified systems, measurements, 149-ISI Coiled conformation, polyelectrolytes in high-ionic-strength solutions, 367 CoL(X) isomers, comparison, 2421 Competition kinetics, fast reactions, 38 Complementarity Cytb5 : cytc, 145-146 ET: decay ofRu(llj tris-bpy, 146 Compton absorption, equation, 8 Compton interactions, definition, 36 Computational methods, liquid structure, 268 Concentrated solutions, complications in irradiation, 9-10 Concentration photoexcitation vs. pulse radiolysis, 166167 primary radiolytic species, 304 pulse radiolysis and laser photoexcitation, 161 Concentration gradients, interpretation of kinetic observations, 10 Contact and solvent-separated ion pairs (CIP-5SIP), transition rate constant, 350 Coordination isomerism, primary rae CoL(C01)+, 240 Copper, azurin proteins, 67-73 Counterion(s) global signal rise time, 35 I specific ion pairing and ionic atmosphere relaxation, 219 Counterion dynamics, intramolecular charge shift reaction, 222-224 Counterion effects, ultrafast ET, 350-351 Counterion valence, time dependence of trajectories, 352/ Coupling decay, protein matrix, 54-61 Coupling efficiency, tunneling pathway, 54-SS Coupling strength, distance dependence of ET rates, 360 Critical cluster, ET, 294 Critical nuclearity, growth kinetics, 304 Critical size, cluster coalescence, 304-307
Cross reactions, relation to self-exchange reactions,317-318 Crystals, Na-Hg reduction of [Ni(2,2 ·bipyridine)3](CI04)z, 287-289 Cyclotrons, heavy-ion sources, 48 Cysteine, bipyridine ligands of ruthenium complexes, 103 Cytochrome c intermolecular and intramolecular ET reactions, 322-328 labeled with ruthenium(ll)-polypyridine complexes, 99-110 pulse radiolysis, 66-67 rate and activation parameters for ET reaction, 3241, 3261 redox reactions, 325 volume changes, 325-328 Cytochrome c oxidase electron flow, 61 links between subunits I and II, 60/ Cytochrome c peroxidase (CCP) derivatives, rate constants for reduction,
901 ET reactivity of oxyferryl heme centers, 81-98 flash photolysis, 84-91 formation of stable oxyferryl heme centers, 82 heme pocket showing key catalytic residues, 83/ pH dependence of turnover, 90 pulse radiolysis, 91-92 surface residues and heme superimposed on Ca backbone, 85/ Cytochromes c and b5, electron transfer, 101-102
D D-A distance decay exponential, 124 protein ET rate constants, 54 D-A pair, E...,, 123 De novo redox proteins, design and study, 146-147 Deactivation processes, transient electronic states, 347 Deazariboflavin semiquinone, ruthenium group on surface ofCCP, 86-91 Degradation, photoexcitation vs. pulse radiolysis, 166-167
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
385
Designer radicals, generation ftom primary radicals, 24 Diets-Alder products, chromatographic purification, 182 Direct MLCT absorption, Fe2+(H20)6 complex, 272-273 Direct photodetachment, electron ftom metal to pre-existing cavity, 269 Direct-current (de) conductivity, ionic species in polar solvents, 2 Directional specificity along peptide backbone, LRET, 140 Disproportionation, semiquinone, 303 Distance, ET rate dependence, 173-174 Distance decay ET coupling zones, 59/ tunneling-pathway model, 58/ Donor-acceptor distances, energy-transfer studies, 153-156 Dosimetry, free radical experiment, 10--12 Driving forces, rates of cytochrome c ET reactions, 52-53 Dual pathways, conformationally gated, 261 Dyads absorption spectra, 186-187 NMR spectral assignments, 186 transient absorption, 191/, 192/, 193/ Dynamical solvent effects, rate of CT reactions,333-334
E
E...
experimental data, 125, 126/ weights on donor couplings, 124{ Electrochemical techniques, high-pressure ET reactions, 315-330 Electrolyte effects, intramolecular ET, 219230 Electrolyte relaxation, Sumi-Marcus theory, 219-220 Electromagnetic radiation, energies, 71 Electron-atom pair formation, equation, 341 Electron capture, rate comparison with ET, 146 Electron donor concentration, decay, 306/, 307/,308/ Electron guns photocathode, 2 RF photocathode, 45-47
Electron-hole recombination porphyrin radical cation and semiquinone, 78 rate constant, 196 Electron hydration, equation, 341 Electron hydration channel, fully relaxed state, 346 Electron(s) in water, dose-depth profiles, 37/ Electron isomerism, C02-binding systems, 240 Electron linac, charged particles, 43-45 Electron machines, Van de Graaff generators used for radiolysis, 42 Electron paramagnetic resonance (EPR), ET rate vs. motion of counterions, 224 Electron photodetachment, equation, 341 Electron photodetachment channel IR high excited CTTS states, 346-347 ultrafast recombination reactions, 341 Electron photodetachment steps, aqueous ionic solute, 340--349/ Electron-proton transfer, dynamics, 340 Electron pulse, species involved in ET, 297 Electron transfer (ET) free-energy dependence, 99-110 mechanism, 302-303 photochemistry and radiolysis, 3 photoinduced, 177-218 pulse radiolysis of proteins, 65-79 rate and activation parameters, 3201 rates, 51 specific ion pairing and ionic atmosphere relaxation, 219 synthetic three-helix bundles, 146-147 Electron transfer kinetics bifunctional redox protein maquettes, 145-159 redox potential of short-lived metal clusters, 293-294 solution catalyzed by metal clusters, 293-314 Electron-transfer pathways cytochrome c covalently bound to ruthenium complex, 108 Tl Cu and T3 copper pair, 78/ Electron transfer pathways, through space (TS) and through peptide backbone (TB), 131 Electron transfer rate 1,4-ee-BCN in THF, 2221 free-energy change, 163/ function of polarity, 172/ presence of counterions, 223/
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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386
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
Electron transfer rate constants, function of free-energy change, 170}-171/ Electron transfer reactions competition with coalescence, 305-306 high pressure, 315-330 Electron tunneling engineered protons, 51-63 ETmodel,lll-120 tightly grouped families of pathways, Ill two-state bridge expanded as sum of pathways, 113/ Electron tunneling coupling in protein, computation, 11 Electron-water couplings, time dependence,336 Electronic coupling engineered proteins, 54-61 norborane-based molecules, 173 protein efficiencies, 57-61 ruthenium-modified derivatives of azurin, 120 virtual route through protein matrix, 115-120 Electronic relaxation, equation, 341 Electronic relaxation channels, UV-IR pulses in liquid water, 338 Electronic tr~itions, effects of solvents, 267 Electrostatic acceleration, schematic representation, 40f Electrostatic energy, transferring an electron, 269 Electrostriction, oxidation ofRu(ll) ammine complexes, 327 Elementary charge transfer, comparative analysis ofH-D isotope effects, 339/ Emission decay, biexponential, 373 Energetics, dyads and triads, 193-194 Energy absorption, physical processes, 8 Energy capture by charge separation, photoexcited molecule, 161, 162f Energy deposition chemical change produced, 9 high-energy electromagnetic radiation, 8 Energy deposition interactions, relative distance, 36-37 Energy levels, initial charge-separated species, 189 Energy storage efficiencies, 161-162 excited-state species, 231-232 Marcus electron transfer theory, 162 Energy transfer, maquettes, 153-156
Engineered metalloproteins and peptides, studies, 156-158 Engineered protons, electron tunneling, 5163 Enzymatic activity dismutation rates of Or. 248 maximal activity, 77 Escherichia coli, manganese superoxide dismutase, 247-262 Escherichia coli MnSOD kinetic traces produced in pulse radiolysis, 258f structure, 257 Excess electron microprobe, 335 ultrashort-lived prehydrated state, 337 Exchange repulsion, solvated electron and electrons bound in solvent molecules, 270 Excited CTTS states, ultrashort-lived transitions, 346 Excited electronic states, ion-solvent couplings and ion-ion interactions, 341 Excited-state species, transition metal complexes, 231-232, 234-235 Exothermic intramolecular ET, ion-pairing control, 222-224 F Fast digitizing oscilloscopes, pulse radiolysis, 174 Fast proton transfer, long-lived charge separation, 17 8 Fe2+(H10)6, primary process in photooxidation, 263-277 Febetrons, Marx-bank impulse generator, 43 Femtosecond photoinduced ET processes, ionic strength, 348}-349/ Femtosecond spectroscopy, !IPPiications, 332 Femtosecond UV excitation of aqueous NaCI solution dynamics of primary ET processes, 343/ transient electronic configurations, 344/ UV-near-IR spectroscopic data, 342/ First-order rate constants, LRET in linear peptides, 133t Flash photolysis CCP,84-91
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
387
compared to pulse radiolysis, 233-234 ET reactivity of oxyferryl heme centers, 81-98 Ni(2,2 •-bipyridine)2+ fonnation, 289-290 photoredox reagents, 86 ruthenium-modified helical maquettes, 148-149 Flexible linker, distribution of distances, 155 Fluorescence, triads and dyads, 187-197 Fluorescence-detected magnetic resonance (FDMR), reactivity of radical cations, 2 Fluorescence lifetimes and amplitudes of triads, 187t Free energy of reaction, independence, 105-107 Free radicals, mechanism and rate constants of reactions, 12-24 Free-energy change charge shift reactions, 169-171 ET reaction, 168/ pulse radiolysis and laser photoexcitation, 161 temperature independence, 169/ Free-energy dependence, rate constants for intramolecular ET, 99-110 Free-energy profiles, peptide isomers, 138/ Fricke dosimeter, product yields or reactant consumption, II
G
G value, radiation chemical yields, 11-12 Gamma rays disintegration of 60Co nuclei, 8 sources for radiolysis, 37-39 Geminate recombination equation, 343 ion pairs in particle tracks, 14 Ground- and excited-state couples, energetics, 238/ Growing Hamiltonian, 118/ Growth nucleus, critical cluster of silver, 294
H H2, photoproduction, 236 Halide ions electrolyte solutions, 333 one-photon allowed p ~ s CTTS transition, 266
Helical secondary structure, effect on ET rates, 145 Helical structures, covalent pathways, 5657 Helicity, effects of solution conditions, 153/ Heme-binding four-helix bundle, ET and catalytic studies, 157 Heme iron, screened from surface charges in oxidized state, 329 Heme peroxidase catalysis, efficiency, 8284 Heme reduction, absorbance changes, 92 His, reactivity of peroxidases with H20 2, 82 His-modified systems, effect of pressure on distant electronic coupling, 328 Hole-burning experiments, ground state of hydrated electron, 33 8 Horse heart cytochrome c, ET with rat liver cytochrome b5 , I 01-102 Horse heart Mb, redox activity, 93 Horseradish peroxidase (HRP), fonnation of stable oxyferryl heme centers, 82 H-Trp-(Pro )n--Tyr-OH peptides, confonnational parameters, 135/ Hydrated electron bleaching and absorption dynamics, 338 conversion to less aggressive ag'.'nts, 66 hydroxyl radical reactions, 22 reducing agent, 15-22 relaxation dynamics, 338 ultrafast spectroscopy, 335-340 Hydrated silver clusters, redox potentials, 308-310 Hydride complex conversion of metallocarboxylic acid, 244 rate-detennining step for fonnation, 243 Hydrogen atom, reactions, 19-21 Hydrogen bonding driving force for ET, 188 effect on lifetime of intennediate state, 190-191 electronic-coupling efficiencies, 57 Hydrogen ion, reduction potentials, 232, 233/ Hydrogen-bond couplings, variation of coupling path length, 55f Hydrogen-bond interactions, long-range ET reactions, 56 Hydrogen-deuterium (H-D) isotope substitution, nonequilibrium electronic states, 339-340 Hydroperoxyl radical, reactions, 28-29 Hydroquinone bielectronic electron donor, 300-301
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
388
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
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optical absorption spectra, 296/ threshold potential for developability, 312 1-Hydroxy-1-methylethyl radical, reactions, 26-28 Hydroxyl radical, reactions, 21-22
Incident laser pulse, photocathode electron gun,46 Inelastic interactions, charged particle penetration, 9 Infrared electron relaxation, deactivation rate,337-338 Inhomogeneous distribution, charge pairs and excited species, 9 Inner-sphere ET reaction, pressure, 321 Inner-sphere mechanisms, inorganic ET reactions, 318-321 Inorganic complexes, photooxidation, 266 Inorganic radicals, aqueous solution, 24t Interconversion mechanism, electron-atom pairs, 350-351 Interference effects, sum of pathways, 114 Interfering tubes, electron tunneling, 11 5 Intermediates, rise and decay time constants, 190 Internal hydrogen bond, dynamics of photoinduced ET and charge recombination, 191 Internal metal 3d --. 4s absorption, aqueous ferrous ion, 265 Internal metal center, design, 157 Internal vibration, ET rate constants, 107108 Intramolecular charge shift reaction, rate dependence on counterion size, 222224 Intramolecular ET azurins, 67-73 driving-force dependence of rate constants, 53/ electrolyte effects, 219-230 observed rate constants, 90 pulse radiolysis and laser photoexcitation, 161-176 rate constants and driving forces, 52t rate constants and free-energy change, 6/ Intramolecular LRET azurins, 70-73 driving force, 71 Intramolecular reduction of Cu(lij by RSSR-, kinetic and thermodynamic data, 7lt
Inverted region demonstration of reality, 5-6 noninverted decay channel, 54 reaction rates, 52-54 Invisible photoproducts, characterization, 235-237 lon(s), mechanism and rate constants of reactions, 12-24 Ion beams, tandem Van de Graaff accelerators, 48 Ion-pair formation, equilibrium constants and thermodynamic parameters, 320t Ion pairing lifetime of charge-separated state ofpANTP,229 photoinduced charge-separated species, 224-229 Ion-solvent molecular couplings, behavior ofCTTS states, 333 Ionic relaxation, Sumi-Marcus theory, 219220 Ionization potential bare and solvated clusters, 309 influence of environment, 310-312 Ionizing radiation interactions, 1 types and interaction with matter, 36-37 Ipso adduct, aromatic species, 22 Iron, complexed with bipyridine ligands, 147 Isomerization bound H01, 254 pH-dependent, 256 superoxide radical, 247 zwitterionic forms of peptides, 134 K
Kinetic energy, electron confined in solvent cavity, 269-270 Kinetics ET in solution catalyzed by metal clusters, 293-314 resolution by numerical simulation, 306307
L
Labyrinth, radioactive source structure, 38 Laccase, electron-uptake site, 74 Lamellar heterostructures, transmission electron microscopy, 359 Laser flash photolysis absorbance change, 88.f-89/
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
389
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Indexes [Ni(2,2' -bipyridine)3](CI04) 1 and TEA in MeCN, 285-286 Laser photoexcitation intramolecular ET, 161-176 strengths, 165-167 Laser photolysis ET reactions in solutions of electrolytes, 219-230 free charge-separated species, 221-222 Laser technology, development, 2 Ligand, redox potential, 311 Linear accelerators advantages and disadvantages, 44-45 charged particles, 43-45 diagram, 44/ Linear energy transfer (LET), production of radical and ionic species in solution, 9 Liquid structure analysis of solvent cavities, 271 computational methods, 268 Long-distance ET processes high-pressure kinetic and thermodynamic techniques, 321-328 metal complexes and cytochrome c, 315330 Long-lived charge separation, increased yield, 196 Long-range electron transfer (LRET) best-fit rate constants, 140/ distance dependence of the rate, 136-139 oxidases as models, 73-77 pathways in azurins, 70-73 proline-bridged aromatic amino acids, 131-143 rate bridge length dependence, 134/ rate in short-bridged peptides, 133 Trp• -+ Tyre and metallic redox systems, 140-141 Long-range electron transfer (LRET) pathways, modeling in peptides, 136-140 Low-oxidation-state chemistry, organometallic dogma, 243
M
M-P,.-V maquettes, putative structure, 148/ Macromolecules, pulse radiolysis, 66-67 Manganese superoxide dismutase, E. coli, 247-262 Maquettes, ruthenium-modified, 148-149 Matrix partitioning, renormalization, 116118
MDESA-Ru(bpy)rMV triad system, redox potential diagram, 371/ Membrane proteins, branching ratio, 360 Metal centers, internal vibrational modes, 107-108 Metal clusters, ET kinetics in solution, 293-314 Metal-ligand binding energy, redox potential, 311 Metal-to-ligand charge transfer (MLCT) aqueous ferrous ion, 265 excited states, 235 photooxidation to Fe3•, 263 Metallo redox centers, -(Pro),.- bridged, 141 Metallopeptide, parallel p-pleated sheet structure, 157-158 Metalloprotein donor-acceptor distances, 155 ET between redox sites, 99 Microwave and de conductivity, electron and ion migration in nonpolar media, 2-3 Mn2+ Complexes rate constants for superoxide radical reactions, 2561 reactions with HOz-(>2-, 255-257 Mn(ll)TTHA complexes characterization, 250-257 equilibrium constants for reactions of 0 2-JH02 radicals, 2541 species produced upon reaction ofHOr oz-, 251/ Mn1ltthaW", rate constants for reaction with oz-, 2521 Mn°SOD and olk.:..c vs. pH, 260/ mechanism, 259-261 Model peptides, Trpe -+ Tyre( radical transformation, 132-133 Molecular hydrogen, photoproduction, 264 Molecular orientation, electronic couplings, 174 Molecular pathways for ET, conformational properties ofpeptides, 137 Molecular triad, photoinduced electron and proton transfer, 177-218 Molten globular proteins, behavior, 156 Monomeric (-helices, ET properties, 156157 Monte Carlo simulations, generation of potential surfaces, 268 Multilayer composites ellipsometric data, 368/ high-surface-area silica, 361
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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390
PHOTOCHEMISTRY AND RAIJIATION CHEMISTRY
organic-inorganic, 359-379 Multilayer thin films anionic sheets with cationic polyelectrolytes, 359 layering procedure, 364-365 technique for growing, 360--361 thickness evolution, 367 Multistep ET, triad, 178 Multisubunit redox enzymes, bond connections, 61 Mutants azurin, 67-73 CCP and HRP, 82 protein structure, 70 Myoglobin ET reactivity of oxyferryl heme centers, 81-98 pulse radiolysis studies, 92-95 N
0 Oligoprolines, parameters ofLRET, 132 Onion structures, microstructure, 366-367 Optical spectrum, pulse radiolysis monitoring, 66 Organic-inorganic multilayer composites, electrostatically constructed, 359-379 Oscillating electric field, acceleration, 40/ Outer-sphere ET reaction, volume profile, 321 Outer-sphere mechanisms, inorganic ET reactions, 318-321 Overlap integrals, HOMOs of indolyl radical and phenol rings, 139 Oxene ligand mechanism of proton delivery on reduction, 92 protonation, 81 Oxidases, models for optimized LRET, 7377
Nanosecond transient diffuse reflectance and transient fluorescence instrumentation, 365/ Naphtazarin hydroquinone, redox potential, 294 Naphtazarin quinone, optical absorption spectra, 296/ Naphtazarin solution kinetics, 297-298 transient absorbance, 298/ Natural photosynthetic systems, long lifetimes of charge-separated states, 360 Ni(2,2 ·-bipyridine)32+ electrochemistry in acetonitrile or dimethylformamide, 280--281 sodium-amalgam reduction, 284-285 Ni(2,2' -bipyridine)n2•, photoreduction of C02, 279-292 [Ni(2,2' -bipyridine) 3](C104) 2, optical spectrum during photolysis, 283/ Nickei(O) complexes, catalysts, 279-280 Nonsymmetrical ET reactions, redox product formation, 318-321 Normal hydrogen electrode (NHE), reduction potentials, 232, 233/ Nuclearity cluster properties, 293 dependence of cluster potential, 294 silver cluster(s), 299 silver cluster redox potential, 308-310, 312 Numerical simulation, QH2 decay, 306-307
Oxidation-reduction processes, Fe2•-Fe3+ couple, 263-264 Oxidation states, unstable, 238-239 Oxyferryl heme centers, reactive intermediates, 81 Oxyferryl heme reactivity, study using radiation and photochemical techniques, 81-98 Oxyferryl heme reduction, comparison of flash photolysis and pulse radiolysis, 95-96 p
Particle accelerators, radiolysis, 39-41 Particle energy, interaction probability, 37 Particle tracks, local inhomogeneities, 9 Pathway approximation, virtual route through protein matrix, 115-120 Pathway scheme, protein, 119-120 Pathway tubes His126-modified azurin, 121, 122/ interference effects, 114 Peptide(s) low-energy conformer, 142/ short-bridged, 141 Peptide bond angles, ~-sheets and ahelices, 56 Peptide-mediated ET, role of conformational equilibria, 151 Peroxidase catalysis, steps involved, 82 pH, influence on ET, 303-304
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
391
Photochemical reactions, transition-metal complexes, 231-245 Photochemically induced charge separation, electrostatically constructed multilayer composites, 359-379 Photochemistry fundamental physical interactions, 6-7 relationship to radiation chemistry, 1-4 Photoconversion process, efficiency, 232 Photodetachment, aqueous ferrous ion, 265 Photoexcitation capabilities for ET, 164-165 specific solutes, 66 Photoexcited charge separation and recombination, dependence ofET rates on !:J.G0 ,J70-171 Photographic developer critical nuclearity of supported clusters, 312 silver cluster potential and potential threshold, 294 Photographic plate, discoveries ofX-rays and radioactivity, I Photoinduced charge separation, rateenergy leveling, 53-54 Photoinduced charge-separated species, ion pairing, 224-229 Photoinduced electron and proton transfer, molecular triad, 177-218 Photoinduced electron transfer, singlet to charge-separated state, 177 Photolysis, definition, 35-36 Photolyze, definition, 8 Photon excitation, equation, 341 Photon-harvesting polymers, hybrid energylET cascades, 376 Photooxidation, Fe2+(H20)6 in water, 263277 Photooxidation of aqueous ferrous ion mechanisms, 265-267 possible primary steps, 269-274 Photoredox chains, additional donor and/or acceptor layers, 376 Photoredox reagent, ideal, 96 Photoredox systems, self-assembling and microheterogeneous, 360 Photoreduction, C02 with Ni(2,2 'bipyridine)n2+ complexes, 279-292 Physical dosimeter, current-measuring device, 12 Picosecond barrier, pulse radiolysis, 46-47 Polarity, ET rate dependence, 171-172 Polaronic CTTS mechanism, calculation, 274
Polyacrylate, behavior of silver clusters, 311 Porphyrin electron-hole recombination, 178 synthesis, 181 Precursor formation, outer-sphere ET processes, 319 Preequilibrium protonation, pH and H-D kinetic solvent isotope effects, 95 Pressure effect on chemical reactions, 316 kinetics and thermodynamics ofET reactions, 315-330 Pressure deceleration, ET steps, 321 Pressure dependence, mechanism ofET process, 328 Primary radicals manipulation, 15 radiolysis of aqueous solutions, 15, 16/ radiolysis of liquid water, 14t -(Pro)n- bridges, electron transferability, 141 Product yields, free radical experiment, I 012 Proline-bridged aromatic amino acids, LRET, 131-143 Protein(s) tong-range ET, 65-79 tubular breakdown ofET, 111-129 Protein-bound redox, generation, 84 Protein bridge electron tunneling, Ill full Gc1a matrix elements, 127t pathways vs. tubes, 120 Protein complexes, electron transfer, I 01 Protein concentration, rate ofET, 70 Proton(s), pulse radiolysis, 47 Proton migration, hydronium ion to neighboring water molecules, 340 Proton motive force, heterogeneous system, 197 Proton transfer effect on lifetime of intermediate state, 190-191 photoinduced, 177-218 yield of long-lived charge-separated species, 189 Proton transfer process rate constant, 196 reduced electron-hole recombination rate,: 197 ps..:MV2+layer, zero-ionic-strength solution, 374 Pseudomonas aeruginosa azurin
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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392
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
ET pathways from disulfide to copper center, 12! three-dimensional structure of polypeptide backbone, 68f time-resolved absorption changes, 69! Pulse radiolysis applications, 331 association of solvated electron with electrolyte cation, 221 capabilities for ET, 164-165 CCP,91-92 compared to flash photolysis, 233-234 determination of mechanism or reaction rate constant, 12 ET reactions in solutions of electrolytes, 219-230 ET reactivity of oxyferryl heme centers, 81-98 experiments, 174 intramolecular and intermolecular ET reactions, 161-176,322 long-range ET in proteins, 65-79 measurementofETrates,l69-174 myoglobin, 9i-9S one-electron reduction potentials of redox pairs, 6 outer-sphere ET reactions, 5-6 photocathode electron guns, 2, 45-47 photochemical reactions of transition metal complexes, 231-245 picosecond barrier, 46-47 strengths, 167-169 superoxide with Mn complexes, 249 transient absorption data for Co-P••V, 151! transient species, 286 Trp• -+ Tyre radical transformation, 132-133 upper limit on measurement of reaction rate, 149 Pump-probe detection, pulse radiolysis, 174 Pyrrolidine side chains, transitions between equilibrium conformations, 136 Q Quantum molecular simulations, short-lived couplings of solvent molecules, 341 Quantum size effect, silver clusters redox properties in solution, 308-310 Quantum yield equations, 10-11 fimil charge-separated species in triads, 194-197
Quenching •RuL3,86 ·Ru(bpy)r ions, 373 Quinone, synthesis, 182
R
Radial distribution function, ferrous ion in aqueous solution, 269f Radiation chemical yields, G value, 11-12 Radiation chemistry fundamental physical interactions, 7-10 mechanistic study of complex photochemical systems, 233 principles and applications, 5-33 relationship to photochemistry, 1-4 Radiation exposure, occupational, 37-38 Radiation sources, historical development, 2 Radicals designer, 24 superoxide,247-262 Radiolysis definition, 35 particle accelerators, 39-41 Radiolysis dosimeter, thiocyanate, 23-24 Radiolysis experiments, design, 35-50 Radiolysis of aqueous solutions, primary products, 91 Radiolyze, definition, 8 Rat liver cytochrome b, ET with horse heart cytochrome c, 101-102 Rate constants azide radical reactions, JOt hydrogen atom reactions, 20t 1-hydroxy-1-methylethyl radical reactions, 21t hydroxyl radical reactions, 2lt Mn and Oi concentrations, 259 radiolysis of pure liquid water, 1St reactions of carbon dioxide radical anion, 2St reactions of radical species, S-6 reduction of substrates by hydrated electrons, 17t
selfreaetions ofH02"/0t. 29/ where to find information, 30-32
~nergy
leveling, photoinduced charge separation, 53-43 Reaction dynamics analysis at microscopic level, 334-335 subpicosecond time scale, 331 Redox-active polymers, deposition onto high-surface-area silica, 367-370
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
393
Redox potential charged cluster, 30 l influence of environment, 310-312 size dependence of metal clusters, 293 Redox-potential diagram, sequence ofET events in composites, 369, 371/ Redox properties of metal clusters, size dependence,308-310 Redox proteins, pulse radiolysis, 67 Redox reaction, Co(terpy)l+ and Co(bpy)/+, 319 Reduced species, nature, 286-289 Reduction(s), pulse-radiolytic, 68 Reduction and reoxidation, superoxide, 247 Reductive quenching, sacrificial reagents, 235 Reference triad, selection, 189-190 Renormalization, electron tunneling bridge, ll6-ll8 Reorganizational energy cytochrome c, 108-109 cytochrome c-b5 system, 101-102 driving-force dependence of rate constants, 95 ET between ruthenium complex and heme iron, 99 Zn-porphyrin center, 93 RF photocathode electron guns advantages and disadvantages, 47 diagram, 46/ pulse radiolysis, 45--47 Rotations, Tyr side chain, 134-135 Ru(II) polymer luminescence, ET quenching, 359 Ru11 (l6-mer) 3-AEDANS, distributional fluorescence lifetime fit, 15 5/ Ru(bipyridine)/+, characterization, 236237 Ru(bipyridine)32+ complex, photoredox chemistry of derivatives, 100 Ruthenium complexes absorbance change vs. time following pulse radiolysis, 94f binding domain for cytochrome c, 102 binding of cytochrome c to other proteins, I OJ-I 05 covalent attachment to His surface, 93 intermolecular and intramolecular ET reactions, 322-328 rate and activation parameters for ET reaction, 324t volume changes, 327 Ruthenium complexed with bipyridine ligands, 147
covalently bound to surface histidines, 81-98 Ruthenium-complex excited state, rapid decrease in absorbance, l 05 Ruthenium polypyridine complexes, rate constants for intramolecular ET reactions, I 05
s Salt concentration, association process, 227-228 Sample degradation, pulse radiolysis and laser photoexcitation, 161 Scavenger concentration, reducing radicals, 299 Secondary structure, effect on ET rates, 151-153 Self-exchange ET reactions relation to cross reactions, 317-318 theoretical modeling, 317 Self-exchange rate, unstable photoproducts, 238-239 Semiquinone electron donor, 302 monoelectronic electron donation, 301 Shielding schemes, radioactive sources, 38 Short-lived prereactive steps, solutions, 331-357 Silica, deposition of redox-active polymers, 367-370 Silver and naphtazarin solutions kinetics, 298-303 transient optical absorption signals, 300/ Silver clusters behavior from electron donor to electron acceptor, 312 kinetics ofET in solution, 293-314 quantum size effect ofnuclearity and redox properties in solution, 308-310 Silver in solution, transient optical adsorption signal, 305/ Size dependence, redox properties of metal clusters, 308-310 SN 1 ionization reaction in polar liquid, 353/ Sodium-amalgam reduction Ni(2,2' -bipyridine)/+, 284-285 Ni(2,2'-bipyridineMC104) 2 in MeCN, 285/ Solar energy, conversion to stored energy. or electricity, 232/ Solute concentration, energy absorption, 910
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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394
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
Solution(s) time dependence of elementary chemical processes, 332f ultrafast ET and short-lived prereactive steps, 331-357 Solution ET theory, background, 333-335 Solvated electron, photooxidation of ferrous ion, 264-265 Solvation shells, anions, cations, and excess electrons, 350 Solvent(s), water, 13-15 Solvent bridge bonding, dynamics of water molecules, 350 Solvent cage, ground or excited states, 332333 Solvent-cage effects chemical processes in polar liquids, 351 equation, 341 interactions of halide ions with polar solvent molecules, 340 Solvent cavities, location in liquid, 269 Solvent dynamics, energy surfaces, 333334 Solvent polarity, ET rate dependence, 171172 Solvent shift electronic spectra, 274 evaluation method, 275 magnitude when complex is placed in water, 272 MLCT, 267, 273/ Spacer group, electronic couplings, 173 Spectroscopic methods high-pressure ET reactions, 31 S-330 time-resolved, 332 Spectroscopy, common techniques, 2 String of pearls, path breakdown of effective C-C coupling, 117/ Sum of pathways, interference effects, 114 Sumi-Marcus 2D free-energy surface concept, adaptation for intramolecular ET, 220{ Supercritical clusters autocatalytic ET, 302 ET, 294 Superexchange coupling model, protein matrix, 54-61 Supermolecules, synthesis, 360 Superoxide, manganese complexes, 247262 Superoxide dismutase (SOD), redox-active metal in active site, 248 Superoxide radical, reactions, 28-29 Support, clusters in solution, 311-312
Surfactant, behavior of silver clusters, 311 Synchrotron, intense source ofX-radiation, 38-39 Synthetic control, probe of mechanism, 239--240
T Temperature, ET rates, 172-173 Terminal amino acids, reversed order, 140 Tetrahydrofuran (THF), electrostatic interactions between ions, 220 Therapeutic agent, MnSOD, 261 Thermal melts, Ru 11-P 16- V and Co111 -P 16V,l56 Thiocyanate optical absorption spectrum in aqueous solution, 23/ radiolysis dosimeter, 23-24 Three-helix bundles, analyses of de novo proteins, 14Crl47 Through-bond ET, evidence, 173 Time resolution, pulse radiolysis and laser photoexcitation, 161 Time scales, measurements made by photoexcitation and pulse radiolysis, 165166 Time window, excited-state lifetime, 145 Time-resolved absorption, rise and decay of an intermediate, 190-193 Track, definition, 35 Trans --+ cis isomerization, Trp-Pro bond, 134 Transient absorption data for Fe-P 12-V, pulse radiolysis, 150f Transient couplings, photoexcitation of aqueous halide, 333 Transient species, rate offormation in Mn(II)TTHA, 250 Transition energy, electron in preexisting solvent cavity, 270 Transition-metal complexes, mechanisms of photochemical reactions, 231-245 Transition moment profile, cavity to water radial distribution functions, 271 Transition state ET process, 321 forward and reverse processes, 323-325 locations along reaction coordinate, 316 Transition state theory, frequency of f3 --+ a transitions, 136 Translational diffusion of ions, SumiMarcus theory, 219-220
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
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Indexes
395
Triads absorption spectra, 186-187 construction routes, 181-186 decay-associated fluorescence emission spectrum, 188/, 189/ decay of transient absorption, 195/ NMR spectral assignments, 186 quantum yields and lifetimes of longlived charge-separated species, 195t transient states and related decay pathways, 194/ Triethylenetetraminehexaacetate (ITHA), mononuclear Mn8 complexes, 247262 Trp• --. •Tyr( radical transfonnation, model peptides, 132-133 Trp-(Pro),-Tyr peptides, confonnational properties, 133-136 Tubes, electron tunneling; 111 Tubular breakdown electron tunneling in proteins, 128 ET in proteins, 111-129 Tunneling electron, magnitude of ionization energy, 73 Tunneling energy, jJ-strand calibration, 123-128 Tunneling path decay, growing Hamiltonian, 118 Tunneling path length, heme and His72, 328 Tunneling-pathway model P-sheet long-range couplings, 55 protein matrix, 54-61 Turnover rate constant, adsorption reactions, 302
u Ultradivided metals, ET efficiency, 310 Ultrafast electron-atom pair deactivations, equation, 343, 346 Ultrafast electron transfer counterion effects, 350-351 energy-level diagram, 345/ solutions, 331-357 Ultrafast spectroscopy, hydrated electron, 335-340 Ultrashort laser pulses, photoexcitation of water molecules, 335 Units, free radical experiment, 10-12 Unstable photoproduct, characterization, 237-239
v Van de Graaffaccelerator description, 42 diagram, 41/ tandem, 48/ Van de Graaff generator advantages and disadvantages, 43 structure and use, 41-43 Viologen electrochemically reduced polymers, 373 measurement of C02- addition rate, 149-150 photoreduction quantum yield, 374-375 Viologen complexes, three-helix bundles, 147-156 Viologen transient absorption, persistence in absence of cobalt, 152/ Visible aqueous electrons, transient absorption spectrum, 336f Volume changes intrinsic and solvational components, 316 source, 325-328 Volume profile nonsymmetrical reactions, 328-329 outer-sphere ET reaction, 321 Volumes of activation, forward and reverse processes, 323-325
w Water conversion into OH radicals and hydrated electrons, 66 dynamical properties, 335 H-D substitution effects, 338 ion-molecule reaction, 338 photoreduction, 264 radiation chemistry, 13-15 time-dependence ofET trajectories, 337/ two-photon photodetachment, 266 Well design, radioactive source structure, 38 Wigglers, radiation intensity and energy range, 39
X
Xanthine oxidase, intramolecular ET rates, 74
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
396
PHOTOCHEMISTRY AND RADIATION CHEMISTRY
X-ray(s) discovery, 1 sources for radiolysis, 37-39 X-ray tubes, early research, 38
intramolecular ET reactions, 107/ proposed structure of variant, 104/ ruthenium(II)-polypyridine complexes, 99-110 transient absorbance changes following photoexcitation, 106/
y
z Zwitterionic forms ofpeptides,lowestenergy conformers, 136
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Yeast cytochrome c bound to ruthenium complexes, ET rate constants, 105t covalently attached to rutheniumpolypyridine complexes, 103-105
In Photochemistry and Radiation Chemistry; Wishart, J., el al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1998.
