Reduced Electronic Spaces for Modeling Donor/Acceptor Interactions

Abstract

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 g 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 e15%) 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.

Electron Localization of Anions Probed by Nitrile Vibrations

“…Following the treatments presented previously, 39 we determined the width of the polarons based on the differences of ESP charge distributions between anions and neutrals as well as on the electron density in the SOMO of the anions (Table 2 and Supporting Information Table S1). A full density of the anion SOMO serves as a plausible zeroth-order estimate of the different densities of electrons to the extent that addition of an electron to the neutral does not 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 appreciably polarize the 'core' defined by the occupied neutral orbitals.…”

Canonical-ensemble state-averaged complete active space self-consistent field (SA-CASSCF) strategy for problems with more diabatic than adiabatic states: Charge-bond resonance in monomethine cyanines

“…Scheme 1) and higherenergy "intermediate" structures with different configurations of the charge and pairing degrees of freedom. 55,56 The essential physics was described by Moffitt, who invoked the formamidinum cation as an explicit example. 57 The π orbital system of the formamidinum cation has four π electrons distributed amongst three p orbitals.…”

Electronic coupling for charge transfer in donor–bridge–acceptor systems. Performance of the two-state FCD model

“…31 They found that V DA computed with the twostate model ''involves crucial mixing with intervening bridge states'' and an increasingly larger number of adiabatic states included in the GMH scheme lead to V DA approaching the through-space coupling values. 31 In the paper we consider model D-B-A systems to explore the performance of a two-state FCD scheme. We show that derived V DA values account properly for both the direct and superexchange interactions even when the tunneling gap is small.…”