The microscopic descriptions of electron transfer (ET) reactions given by Marcus theory (MT) and by the intersecting-state model (ISM) are compared with ab initio calculations on O2/O2- and C6H6/C6H6- model systems. The activated configuration calculated by ab initio methods agrees only with that of ISM. Solvent effects in self-exchange rates and in intervalence bands of mixed-valence symmetrical compounds are shown to be smaller than predicted by dielectric continuum models. MT and ISM are used to calculate self-exchange and cross-reaction rates of transition-metal complexes and organic species. It is shown that a compensation of effects may take place in MT calculations. Absolute ET rate calculations using ISM are in good agreement with experiment when non-adiabatic factors are included in σ*(d) electron exchanges. It is shown that ISM reproduces different types of free-energy profiles (Rehm-Weller behaviour, Marcus inverted region, double inverted region) with only one adjustable parameter. The donor-acceptor distance dependence, temperature dependence and free-energy dependence of intramolecular ET reactions are calculated with two adjustable parameters. These calculations are within an order of magnitude of the experimental rates.
FriedmanL. H., HuntJ. P., PlaneR. A., and TaubeH., J. Am. Chem. Soc.73, 4028 (1951).
58.
BakerB. R., BasoloF., and NeumannH. M., J. Phys. Chem.63, 371 (1959).
59.
NavonG., J. Phys. Chem.85, 3547 (1981).
60.
WinklerJ. R., RiceS. F., and GrayH. B., Comments Inorg. Chem.1, 47 (1981).
61.
HushN. S., ACS Symp. Series198, 301 (1982).
62.
BurandaT., LeiY., and EndicottJ. F., J. Am. Chem. Soc.114, 6916 (1992).
63.
SongX., LeiY., Van WallendalS., PerkovicM. W., JackmanD. C., EndicottJ. F., and RillemaD. P., J. Phys. Chem.97, 3225 (1993).
64.
BuhksE., BixonM., JortnerJ., and NavonG., Inorg. Chem.18, 2014 (1979).
65.
NewtonM. D., J. Phys. Chem.95, 30 (1991).
66.
NelsenS. F., RumackD. T., and Meot-Ner (Mautner)M., J. Am. Chem. Soc.109, 1373 (1987).
67.
PhelpsD. K., RammM. T., WangY., NelsenS. F., and WeaverM. J., J. Phys. Chem.97, 181 (1993).
68.
PhelpsD. K., GordJ. R., FreiserB. S., and WeaverM. J., J. Phys. Chem.95, 4338 (1991).
69.
MautnerM., J. Am. Chem. Soc.111, 2830 (1989).
70.
KeeseeR. G., and CastlemanA. W., J. Phys. Chem. Ref. Data15, 1011 (1986).
71.
McManisG. E., NielsonR. M., GochevA., and WeaverM. J., J. Am. Chem. Soc.111, 5533 (1989).
72.
ChanM.-S., and WahlA. C., J. Phys. Chem.86, 126 (1982).
73.
LiT. T.-T., and BrubakerC. H.Jr., J. Organometallic Chem.216, 223 (1981).
74.
MarcusR. A., and SiddarthP., in Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory, KochanskiE. (ed.), NATO ASI Series, Kluwer, Dordrecht, (1992), p. 49.
75.
BurgessJ., and PelizzettiE., Prog. Reaction Kinetics17, 107 (1992).
76.
NielsonR. M., and WherlandS., Inorg. Chem.23, 1338 (1984).
77.
GramppG., and JaenickeW., Ber. Bunsenges. Phys. Chem.95, 904 (1991).
78.
EbersonL., Adv. Phys. Org. Chem.18, 79 (1982).
79.
KowertB. A., MarcouxL., and BardA. J., J. Am. Chem. Soc.94, 5538 (1972).
80.
NelsenS. F., KimY., and BlackstockS. C., J. Am. Chem. Soc.111, 2045 (1989).
81.
HushN. S., Prog. Inorg. Chem.8, 391 (1967).
82.
HushN. S., Electrochim. Acta13, 1005 (1968).
83.
TomG. M., CreutzC., and TaubeH., J. Am. Chem. Soc.96, 7827 (1974).
84.
HuppJ. T., DongY., BlackbournR. L., and LuH., J. Phys. Chem.97, 3278 (1993).
85.
BlackbournR. L., and HuppJ. T., J. Phys. Chem.1990, 1788 (1990).
86.
NelsenS. F., AdamusJ., and WolffJ. J., J. Am. Chem. Soc.116, 1589 (1994).
87.
MarcusR. A., J. Chem. Phys.43, 679 (1965).
88.
NelsenS. F., RammM. T., WolffJ. J., and PowellD. R., J. Am. Chem. Soc.119, 6863 (1997).
89.
HammackW. S., DrickamerH. G., LoweryM. D., and HendricksonD. N., Inorg. Chem.27, 1307 (1988).
90.
HammackW. S., DrickamerH. G., LoweryM. D., and HendricksonD. N., Chem. Phys. Lett.132, 231 (1986).
91.
MiyasakaH., KotaniS., ItayaA., SchweitzerG., De SchryverF., and MatagaN., J. Phys. Chem. B101, 7978 (1997).
92.
HorneR. A., J. Inorg. Nucl. Chem.25, 1139 (1963).
93.
KarlströmG., and MalmqvistP.-Å., J. Chem. Phys.96, 6115 (1992).
94.
Meot-Ner (Mautner)M., and NetaP., J. Phys. Chem.90, 4648 (1986).
95.
TakanoT., and DickersonR. E., J. Mol. Biol.153, 79 (1981).
96.
TakanoT., and DickersonR. E., J. Mol. Biol.153, 95 (1981).
97.
MatsuuraY., TakanoT., and DickersonR. E., J. Mol. Biol.156, 389 (1982).
98.
MerghuisA. M., and BrayerG. D., J. Mol. Biol.223, 959 (1992).
99.
ZhouH.-X., J. Am. Chem. Soc.116, 10362 (1994).
100.
ChurgA. K., WeissR. M., WarshelA., and TakanoT., J. Phys. Chem.87, 1983 (1983).
101.
MueggeI., QiP. X., WandA. J., ChuZ. T., and WarshelA., J. Phys. Chem. B101, 825 (1997).
102.
EkstromA., McLarenA. B., and SmytheL. E., Inorg. Chem.15, 2853 (1976).
103.
KhanS. U. M., and ZhouZ. Y., J. Chem. Phys.93, 8808 (1990).
104.
SuppanP., Topics Current Chem.163, 95 (1992).
105.
ChandlerD., and KuharskiR. A., Faraday Disc. Chem. Soc.85, 329 (1988).
106.
RauhutG., and ClarkT., J. Am. Chem. Soc.115, 9127 (1993).
107.
RauhutG., and ClarkT., J. Chem. Soc. Faraday Trans.90, 1783 (1994).
108.
JakobsenS., MikkelsenK. V., and PedersenS. U., J. Phys. Chem.100, 7411 (1996).
109.
NielsonR. M., HuppJ. T., and YoonD. I., J. Am. Chem. Soc.117, 9085 (1995).
110.
GeorgeP., and GriffithJ. S., in The Enzymes, BoyerP. D., LardyH., and MyrbäckK. (eds.), Vol. 1, Academic Press, New York, (1959), p. 347.
111.
SutinN., Prog. Inorg. Chem.30, 441 (1983).
112.
NewtonM. D., and SutinN., Ann. Rev. Phys. Chem.35, 437 (1984).
113.
VaskaL., Acc. Chem. Res.9, 175 (1976).
114.
FormosinhoS. J., in Theoretical and Computational Models for Organic Chemistry, FormosinhoS. J., CsizmadiaI. G., and ArnautL. G. (eds.), NATO ASI, Kluwer, Dordrecht, (1991), p. 159.
115.
LeeC.-Y., and DePristoA. E., J. Am. Chem. Soc.105, 6775 (1983).
116.
JortnerJ., J. Am. Chem. Soc.102, 6676 (1980).
117.
HinshelwoodC. N., Chem. Soc. Rev.27, 20 (1930).
118.
EvansM. G., and PolanyiM., Trans. Faraday Soc.31, 875 (1935).
119.
EvansM. G., Trans. Faraday Soc.35, 824 (1939).
120.
PaulingL., J. Am. Chem. Soc.69, 542 (1947).
121.
AgmonN., and LevineR. D., Chem. Phys. Lett.52, 197 (1977).
122.
AgmonN., Int. J. Chem. Kinet.13, 333 (1981).
123.
ScandolaF., and BalzaniV., J. Am. Chem. Soc.101, 6140 (1979).
124.
BalzaniV., BollettaF., and ScandolaF., J. Am. Chem. Soc.102, 2152 (1980).
125.
VarandasA. J. C., and FormosinhoS. J., J. Chem. Soc., Faraday Trans. 282, 953 (1986).
126.
ArnautL. G., and FormosinhoS. J., in Homogeneous Photocatalysis, ChanonM. (ed.), J. Wiley & Sons, New York, (1997), p. 55.
127.
FormosinhoS. J., J. Chem. Soc., Perkin Trans. 2, 61 (1987).
128.
FormosinhoS. J., and GilV. M. S., J. Chem. Soc., Perkin Trans. 2, 1655 (1987).
129.
FormosinhoS. J., Tetrahedron43, 1116 (1987).
130.
ArnautL. G., and FormosinhoS. J., J. Phys. Chem.92, 685 (1988).
131.
FormosinhoS. J., and ArnautL. G., J. Chem. Soc., Perkin Trans. 2, 1947 (1989).
132.
YatesK., J. Phys. Org. Chem.2, 300 (1989).
133.
FormosinhoS. J., J. Phys. Org. Chem.3, 325 (1990).
134.
ArnautL. G., and FormosinhoS. J., J. Phys. Org. Chem.3, 95 (1990).
135.
ArnautL. G., J. Phys. Org. Chem.4, 726 (1991).
136.
ArnautL. G., and FormosinhoS. J., J. Photochem. Photobiol. A: Chem.69, 41 (1992).
137.
ArnautL. G., in Proton Transfer in Hydrogen-Bonded Systems, BountisT. (ed.), Plenum Press, New York, (1992), p. 281.
138.
ArnautL. G., and FormosinhoS. J., J. Photochem. Photobiol., A: Chem.75, 1 (1993).
139.
StranksD. R., Pure Appl. Chem.38, 303 (1974).
140.
LaidlerK. J., Theories of Chemical Reaction Rates, McGraw-Hill, New York, (1969), p. 58.
141.
LandauL., Phys. Z. Sowjetunion1, 88 (1932).
142.
ZenerC., Proc. Roy. Soc., (London)A137, 696 (1932).
143.
StueckelbergE. G. C., Helv. Phys. Acta5, 369 (1932).
144.
UlstrupJ., Charge Transfer Processes in Condensed Media, Spinger-Verlag, Berlin, (1979), p. 175.
145.
BurrowsH. D., and FormosinhoS. J., J. Chem. Soc., Faraday Trans. 282, 1563 (1986).
146.
GermanE. D., J. Chem. Soc., Faraday Trans. I81, 1153 (1985).
147.
NewtonM. D., J. Phys. Chem.92, 3049 (1988).
148.
CaveR. J., and NewtonM. D., J. Chem. Phys.106, 9213 (1997).
149.
ZwolinskiB. J., MarcusR. J., and EyringH., Chem. Rev.55, 157 (1955).
150.
MarcusR. J., ZwolinskiB. J., and EyringH., J. Phys. Chem.58, 432 (1954).
151.
MoserC. C., KeskeJ. M., WarnckeK., FaridR. S., and DuttonP. L., Nature355, 796 (1992).
152.
AsahiT., OhkohchiM., and MatagaN., J. Phys. Chem.97, 13132 (1993).
153.
ReynoldsW. L., and LumryR. W., Mechanisms of Electron Transfer, Ronald Press Company, New York, (1966), p. 86.
154.
MillsI. M., in Frontiers of Laser Spectroscopy of Gases, AlvesA. C. P., BrownJ. M., and HollasJ. M. (eds.), NATO ASI, Kluwer, Dordrecht, (1988), p. 461.
155.
SchmidtK. H., and MüllerA., Inorg. Chem.14, 2183 (1975).
156.
HerzbergG., Molecular Spectra and Molecular Structure. II. Infrared and Raman Spectra of Polyatomic Molecules, Van Nostrand Reinhold, New York, (1945), p. 118.
157.
GoodmanL., OzkabakA. G., and ThakurS. N., J. Phys. Chem.95, 9044 (1991).
158.
FormosinhoS. J., Mol. Photochem.7, 41 (1976).
159.
FormosinhoS. J., J. Chem. Soc., Faraday Trans. 270, 605 (1974).
160.
FormosinhoS. J., J. Chem. Soc. Faraday Trans. 272, 1313 (1976).
161.
FormosinhoS. J., and ArnautL. G., Adv, Photochem.16, 67 (1991).
162.
AraiT., TobitaS., and ShizukaH., J. Am. Chem. Soc.117, 3968 (1995).
163.
MahanB. H., J. Chem. Ed.51, 308 (1974).
164.
StrommenD. P., MallickP. K., DanzerG. D., LumpkinR. S., and KincaidJ. R., J. Phys. Chem.94, 1357 (1990).
165.
JonesL. H., J. Chem. Phys.36, 1209 (1962).
166.
GordyW., J. Chem. Phys.14, 305 (1946).
167.
GordonA. J., and FordR. A., The Chemist's Companion, John Wiley, New York, (1972), p. 107 and 114.
168.
MeyerT. J., Acc. Chem. Res.11, 94 (1978).
169.
EbersonL., and ShaikS. S., J. Am. Chem. Soc.112, 4484 (1990).
170.
BernhardP., BürgiH.-B., RaselliA., and SargesonA. M., Inorg. Chem.28, 3234 (1989).
171.
LaChance-GalangK. J., DoanP. E., ClarkeM. J., RaoU., YamanoA., and HoffmanB. M., J. Am. Chem. Soc.117, 3529 (1995).
LarssonS., StåhlK., and ZernerM. C., Inorg. Chem.25, 3033 (1986).
174.
TrasattiS., Pure Appl. Che.58, 955 (1986).
175.
MarcusR. A., J. Phys. Chem.67, 853 (1963).
176.
MarcusR. A., Discuss. Faraday Soc.29, 21 (1969).
177.
FreseK. W.Jr., J. Phys. Chem.85, 3911 (1981).
178.
CampionR. J., PurdieN., and SutinN., Inorg. Chem.3, 1091 (1964).
179.
BennettL. E., and SheppardJ., J. Phys. Chem.66, 1275 (1962).
180.
HydeM. R., DaviesR., and SykesA. G., J. Chem. Soc. Dalton Trans., 1838 (1972).
181.
EndicottJ. F., and TaubeH., J. Am. Chem. Soc.86, 1686 (1964).
182.
PrystasT. J., and SutinN., J. Am. Chem. Soc.95, 5545 (1973).
183.
NarusawaY., KimuraM., and NakanoK., Bull. Chem. Soc. Jpn.47, 2017 (1974).
184.
CandlinJ. P., HalpernJ., and TrimmD. L., J. Am. Chem. Soc.86, 1019 (1964).
185.
BöttcherW., BrownG. M., and SutinN., Inorg. Chem.18, 1449 (1979).
186.
BerkoffR., KristK., and GofneyH. D., Inorg. Chem.19, 1 (1980).
187.
DulzG., and SutinN., J. Am. Chem. Soc.86, 829 (1964).
188.
Ford-SmithM. H., and SutinN., J. Am. Chem. Soc.83, 1830 (1961).
189.
OhsawaY., SagiT., and AoyaguiS., J. Electroanal. Chem.106, 327 (1980).
190.
LinC.-T., BöttcherW., ChouM., CreutzC., and SutinN., J. Am. Chem. Soc.98, 6536 (1976).
191.
BallardiniR., VaraniG., ScandolaF., and BalzaniV., J. Am. Chem. Soc.98, 7432 (1976).
192.
MeyerT. J., and TaubeH., Inorg. Chem.7, 2369 (1968).
193.
JacksC. A., and BennettL. E., Inorg. Chem.13, 2035 (1974).
194.
BockC. R., MeyerT. J., and WhittenD. G., J. Am. Chem. Soc.96, 4710 (1974).
195.
BollettaF., MaestriM., MoggiL., and BalzaniV., J. Chem. Soc., Chem. Commun., 901 (1975).
196.
HaimA., and SutinN., Inorg. Chem.15, 476 (1976).
197.
BodekI., and DaviesG., Coord. Chem. Rev.14, 269 (1974).
198.
BrownG. M., KrentzienH. J., AbeM., and TaubeH., Inorg. Chem.18, 3374 (1979).
199.
BadgerR. M., J. Chem. Phys.1935, 710 (1935).
200.
ArnautL. G., and FormosinhoS. J., J. Mol. Struct. (Theochem)233, 209 (1991).
201.
ArnautL. G., in Molecular Electrochemistry of Inorganic, Bioinorganic and Organometallic Compounds, PombeiroA. J. L., and McClevertyJ. (eds.), NATO ASI Series, Kluwer, Dordrecht, (1993), p. 207.
202.
FormosinhoS. J., Pure Appl. Chem.61, 891 (1989).
203.
MarcusR. A., J. Chem. Phys.26, 872 (1957).
204.
KojimaH., and BardA. J., J. Am. Chem. Soc.97, 6317 (1975).
205.
PeoverM. E., Electrochim. Acta13, 1083 (1968).
206.
SugaK., IshikawaS., and AoyaguiS., Bull. Chem. Soc. Jpn.46, 808 (1973).
207.
MeiselD., and FassendenR. W., J. Am. Chem. Soc.98, 7505 (1976).
208.
JohnsonM. D., MillerJ. R., GreenN. S., and ClossG. L., J. Am. Chem. Soc.93, 1173 (1989).
209.
SugaK., and AoyaguiS., Bull. Chem. Soc. Jpn.46, 755 (1973).
210.
GramppG., CebeM., and CebeE., Z. Physik. Chem. N. F.166, 93 (1990).
211.
NelsenS. F., WangY., PowellD. R., and HayashiR. K., J. Am. Chem. Soc.115, 5246 (1993).
212.
KlimkansA., and LarssonS., Chem. Phys.189, 25 (1994).
213.
HuK., and EvansD. H., J. Phs. Chem.100, 3030 (1996).
214.
NetoN., ScroccoM., and CalifanoS., Spectochim. Acta22, 1981 (1966).
215.
StevensonC. D., and RiceC. V., J. Am. Chem. Soc.117, 10551 (1995).
216.
SzwarcM., in Ions and Ion Pairs in Organic Reactions, SzwarcM. (ed.) Vol. 2, John Wiley & Sons, New York, (1974), p. 61.
217.
DodsonC. L., and GrahamJ. F., J. Phys. Chem.77, 2903 (1973).
NelsenS. F., RammM. T., IsmagilovR. F., NagyM. A., TrieberD. A., PowellD. R., ChenX., GenglerJ. J., QuQ., BrandtJ. L., and PladziewiczJ. R., J. Am. Chem. Soc.119, 5900 (1997).
221.
TrotterJ., Acta Crystallogr.13, 86 (1960).
222.
RaymondK. S., and WheelerR. A., J. Chem. Soc. Faraday Trans.89, 665 (1993).
223.
PeitiläL. O., PalmöK., and MannforsB., J. Mol. Spectrosc.116, 1 (1986).
224.
ChipmanD. M., and PrebendaM. F., J. Phys. Chem.90, 5557 (1986).
225.
TrotterJ., Acta Crystallogr.12, 884 (1959).
226.
KuwaeA., and MachidaK., Spectrochim. Acta35A, 27 (1979).
227.
MalatestaV., MilliniR., and MontanariL., J. Am. Chem. Soc.117, 6258 (1995).
KikuchiK., NiwaT., TakahashiY., IkedaH., and MiyashiT., J. Phys. Chem.97, 5070 (1993).
269.
PetersK. S., Adv. Electron Transfer Chem.4, 27 (1994).
270.
GouldI. R., and FaridS., Acc. Chem. Res.29, 522 (1996).
271.
NiwaT., KikuchiK., MatsusitaN., HayashiM., KatagiriT., TakahashiY., and MiyashiT., J. Phys. Chem.97, 11960 (1993).
272.
BertrandP., Structure and Bonding75, 1 (1991).
273.
AsahiT., MatagaN., TakahashiY., and MiyashiT., Chem. Phys. Lett.171, 309 (1990).
274.
GouldI. R., MoodyR., and FaridS., J. Am. Chem. Soc.110, 7242 (1988).
275.
GouldI. R., and FaridS., J. Phys. Chem.96, 7635 (1992).
276.
GouldI. R., EgeD., MoserJ. E., and FaridS., J. Am. Chem. Soc.112, 4290 (1990).
277.
BurgetD., JacquesP., VautheyE., SuppanP., and HaselbachE., J. Chem. Soc., Faraday Trans.90, 2481 (1994).
278.
GouldI. R., EgeD., MattesS. L., and FaridS., J. Am. Chem. Soc.109, 3794 (1987).
279.
VautheyE., SuppanP., and HaselbachE., Helv. Chim. Acta71, 93 (1988).
280.
MatagaN., AsahiT., KandaY., OkadaT., and KakitaniT., Chem. Phys.127, 249 (1988).
281.
WellerA., Z. Physik. Chem. N. F.133, 93 (1982).
282.
HeinisT., ChowdhuryS., ScottS. L., and KebarleP., J. Am. Chem. Soc.110, 400 (1988).
283.
ClossG. L., CalcaterraL. T., GreenN. J., PenfieldK. W., and MillerJ. R., J. Phys. Chem.90, 3673 (1986).
284.
DeisenhoferJ., EppO., SinningI., and MichelH., J. Mol. Biol.246, 429 (1995).
285.
LoutfyR. O., and LoutfyR. O., Can. J. Chem.54, 1454 (1976).
286.
ClossG. L., PiotrowiakP., MacInnisJ. M., and FlemingG. R., J. Am. Chem. Soc.110, 2652 (1988).
287.
ClossG. L., JohnsonM. D., MillerJ. R., and PiotrowiakP., J. Am. Chem. Soc.111, 3751 (1989).
288.
RothmanW., HirayamaF., and LipskyS., J. Chem. Phys.58, 1300 (1973).
289.
SigmanM. E., and ClossG. L., J. Phys. Chem.95, 5012 (1991).
290.
KadhumA. A. H., and SalmonG. A., J. Chem. Soc. Faraday Trans. 182, 2521 (1986).
291.
ZamaraevK. I., KhairutdinovR. F., and MillerJ. R., Chem. Phys. Lett.57, 311 (1978).
292.
SalmonG. A., Faraday Disc. Chem. Soc.74, 191 (1982).
293.
HolzwarthA. R., and MüllerM. G., Biochem.35, 11820 (1996).
294.
LaporteL. L., PalaniappanD. G., DaviesC., KirmaierC. C., SchenckC. C., HoltenD., and BocianD. F., J. Phys. Chem.100, 17696 (1996).
295.
BeekmanL. M. P., van StokkumI. H. M., MonshouwerR., RijndersA. J., McGlynnP., VisschersR. W., JonesM. R., and van GrondelleR., J. Phys. Chem.100, 7256 (1996).
296.
NagarajanV., ParsonW. W., DaviesD., and SchenckC. C., Biochemistry32, 12324 (1993).
297.
LaporteL., McDowellL. M., KirmaierC., SchenckC. C., and HoltenD., Chem. Phys.176, 615 (1993).
298.
MurchinsonH. A., AldenR. G., AllenJ. P., PeloquimJ. M., TaguchiA. K. W., WoodburyN. W., and WilliamsJ. C., Biochemistry32, 3498 (1993).
299.
WilliamsJ. C., AldenR. G., MurchinsonH. A., PeloquimJ. M., WoodburyN. W., and AllenJ. P., Biochemistry31, 11029 (1992).
300.
BodesheimM., SchützM., and SchmidtR., Chem. Phys. Lett.221, 7 (1994).
301.
HerzbergG., Molecular Spectra and Molecular Structure. I. Spectra of Diatomic Molecules, Van Nostrand, New York, (1950), p. 560.
