Reduced electronic spaces for modeling donor/acceptor interactions

Robert J Cave, Stephen T Edwards, J Andrew Kouzelos, Marshall D Newton
Journal of Physical Chemistry. B 2010 November 18, 114 (45): 14631-41
Diabatic states for donor (D) and acceptor (A) interactions in electron transfer (ET) processes are formulated and evaluated, along with coupling elements (H(DA)) and effective D/A separation distances (r(DA)), for reduced electronic spaces of variable size, using the generalized Mulliken Hush model (GMH), applicable to an arbitrary state space and nuclear configuration, and encompassing Robin-Day class III and as well as class II situations. Once the electronic state space is selected (a set of n ≥ 2 adiabatic states approximated by an orbital space based on an effective 1-electron (1-e) Hamiltonian), the charge-localized GMH diabatic states are obtained as the eigenstates of the dipole moment operator, with rotations to yield locally adiabatic states for sites with multiple states. The 1-e states and energies are expressed in terms of Kohn-Sham orbitals and orbital energies. Addressing questions as to whether the estimate of H(DA) "improves" as one increases n, and in what sense the GMH approach "converges" with n, we carry out calculations for three mixed-valence binuclear Ru complexes, from which we conclude that the 2-state (2-st) model gives the most appropriate estimate of the effective coupling, similar (to within a rms deviation of ≤15%) to coupling elements obtained by superexchange correction of H(DA) values based on larger spaces (n = 3-6), and thus yielding a quasi-invariant value for H(DA) over the range explored in the calculations (n = 2-6). An analysis of the coupling and associated D and A states shows that the 2-st coupling involves crucial mixing with intervening bridge states (D and A "tails"), while increasingly larger state spaces for the same system yield increasingly more localized D and A states (and weaker coupling), with H(DA) tending to approach the limit of "bare" or "through space" coupling. These results help to reconcile seemingly contradictory assertions in the recent literature regarding the proper role of multistate frameworks in the formulation of coupling for both intra- and intermolecular ET systems.The present results are compared in detail with other reported results.

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