Stationary points in the temperature dependence of electron transfer rates
โ Scribed by Dmitry V. Matyushov; Roland Schmid
- Publisher
- Elsevier Science
- Year
- 1994
- Tongue
- English
- Weight
- 524 KB
- Volume
- 220
- Category
- Article
- ISSN
- 0009-2614
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โฆ Synopsis
The temperature dependence of the rate of electron transfer is analyzed in the framework of a molecular theory presented recently, characterized by decoupling the total solvent reorganization energy into two contributions featuring reorganizations of permanent dipoles as well as solvent density. The inclusion of the temperature dependence of liquid density reorganization can give rise to a maximum in the Arrhenius coordinates for electron transfer in the inverted region and for exothermic reactions with small activation barriers as well.
๐ SIMILAR VOLUMES
T, is the temperature at which the surface tension is measured. The density p must also be corrected, using the bulk coeilicient of expansion. Using a factor o = 9 and without making any temperature corrections, relatively good predictions are made for the surface tension of many metals. Table 1
WC h.vc mvcst~zrcd the dependence of rhc clcc~ronw I-actor III clccuon-tnnsfccr ra,e const.~nlr on tic cnmw gap and tcmpualurc by minimizing the clcctronic cncrgy wilh rcspcc~ to the mstanbncous non-equdbrmm solvent polar~~t~on. The clcctronic charge billows out and shrinks III rhc "normal" and slro