Marcus theory and its numerous derivatives, based on a picture of spherical reactants immersed in a continuum solvent, are the primary theoretical models for bimolecular electron transfer reactions in solution. Despite their success, these models completely disregard the molecular nature of liquids, and some of the parameters underlying the theory are not easily accessible by experiment. One such parameter is the electronic coupling matrix element, H_{RP} = <Φ_{R}|H|Φ_{P}>, which is related to the probability of jumping between the diabatic reactant and product states at the crossing region. In order to study the distance and orientation dependence of this parameter, we have performed constrained density functional theory calculations on thousands of electron donor/acceptor pairs generated by molecular dynamics simulations. We find that not only does H_{RP} vary widely for pairs with the same center-of-mass separation *r* (left panel), its average (right panel) does not follow the predicted exponential dependence on *r*. Therefore, one cannot ignore the molecularity of the system if a quantitative description of electron transfer dynamics is desired.

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