2ND-ORDER SURFACE PHASE-TRANSITIONS IN ELECTRODE-KINETICS

Citation
Aa. Kornyshev et al., 2ND-ORDER SURFACE PHASE-TRANSITIONS IN ELECTRODE-KINETICS, Journal of physical chemistry, 100(26), 1996, pp. 11175-11183
Citations number
38
Categorie Soggetti
Chemistry Physical
ISSN journal
00223654
Volume
100
Issue
26
Year of publication
1996
Pages
11175 - 11183
Database
ISI
SICI code
0022-3654(1996)100:26<11175:2SPIE>2.0.ZU;2-C
Abstract
A theory, based on the Landau-Ginzburg formalism, shows that remarkabl e singularities in currents of electrode charge transfer reactions occ ur near the critical potentials where second-order surface phase trans itions take place. This happens if the fluctuations of the order param eter, which describes the transition, are exponentially coupled to the reaction system via fluctuating tunneling or activation barriers. Cou pling depending on the sign of the order parameter is considered; the corresponding singularities in Arrhenius and Tafel plots for electrode currents are predicted, and the perspectives for their experimental i nvestigation are discussed.