Chloride is an essential cofactor in the oxygen evolution reaction that takes place in photosystem II (PSII). The oxygen-evolving complex (OEC) is oxidized in a linear four-step photocatalytic cycle in which chloride is required for the OEC to advance beyond the S-2 state. Here, using density functional theory, we compare the energetics and spin configuration of two different states of the Mn4CaO5 cluster in the S-2 state: state A with Mn1(3+) and B with Mn4(3+) with and without chloride. The calculations suggest that model B with an S = 5/2 ground state occurs in the chloride -depleted PSII, which may explain the presence of the EPR signal at g = 4.1. Moreover, we use multiconformer continuum electrostatics to study the effect of chloride depletion on the redox potential associated with the S-1/S-2, and S-2/S-3 transitions.