Bjerrum pairing correlations at charged interfaces

Electrostatic correlations play a fundamental role in aqueous solutions. In this letter, we identify transverse and lateral correlations as two mutually exclusive regimes. We show that the transverse regime leads to binding by generalization of Bjerrum pair formation theory, yielding binding constants from first-principle statistical-mechanical calculations. We compare our theoretical predictions with experiments on charged membranes and Langmuir monolayers and find good agreement. We contrast our approach with existing theories in the strong-coupling limit and on charged modulated interfaces, and discuss different scenarios that lead to charge reversal and equal-sign attraction by macro-ions.