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36 As a reference point for the pathway calculations, we provide some details here. All Fock matrix elements involving Rydberg and core electrons were set to zero. Additionally, the terms involving antibonding orbitals (for the radical cation) or bonding orbitals (for the radical anion) on the bridging atoms were zeroed out; however, this was found to have a negligible effect upon the overall electronic coupling. This latter finding indicates that the coupling mechanism for radical cations is dominated by hole-mediated superexchange and that for radical anions is dominated by electron-mediated superexchange (at least in these systems). The resulting NBO Fock matrix was diagonalised, and the energy splitting associated with the α HOMO and HOMO-1 levels and β LUMO and LUMO+1 was taken as being equal to 2|V| for the radical cation and anion, respectively.
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