The existence of structural water in the interior of both oxidized and
reduced horse-heart cytochrome c in solution is demonstrated using nu
clear magnetic resonance spectroscopy. Six water molecules have been l
ocated in ferrocytochrome c and five in ferricytochrome c, with reside
nce times greater than a few hundred picoseconds. Two water molecules
are located in the haem crevice, one of which is found to undergo a la
rge change in position with a change of oxidation state. Both of these
observations indicate that buried structural waters in the haem crevi
ce have, by microscopic dielectric effects, significant roles in the s
etting of the solvent reorganization energy associated with electron t
ransfer.