Site Correlations, Capacitance, and Polarizability From Protein Protonation Fluctuations.

We generalize the Kirkwood-Shumaker theory of protonation fluctuation for an anisotropic distribution of dissociable charges on a globular protein. The fluctuations of the total charge and the total dipole moment, in contrast to their average values, depend on the same proton occupancy correlator, thus exhibiting a similar dependence also on the solution pH. This has important consequences for the Kirkwood-Shumaker interaction and its dependence on the bathing solution conditions.