Theory of transient and steady-state ECL generation at double-hemicylinder assemblies using conformal mapping and simulations

Rigorous analytical expressions for steady-state currents and electrogenerated chemiluminescence (ECL) intensities are derived for two-hemicylinder assemblies operating in the ECL generation mode based on a specific conformal mapping transform. This transform is also used for fast and accurate simulations of transient currents and ECL intensities leading to an excellent agreement at long times with the analytical steady state solutions. These results are compared to those relative to two-band assemblies to investigate the effect of hemicylindrical electrode protuberance on ECL efficiencies. This evidence that electrode protuberance results in a drastic increase of the ECL generation and shortening of commutation times when the gap is not too large as compared to the electrode radii. (C) 2003 Elsevier B.V. All rights reserved.