Estimation of electronic coupling in π -stacked donor-bridge-acceptor systems: correction of the two-state model

Comparison of donor-acceptor electronic couplings calculated within two-state and three-state models suggests that the two-state treatment can provide unreliable estimates of Vda because of neglecting the multistate effects. We show that in most cases accurate values of the electronic coupling in a π stack, where donor and acceptor are separated by a bridging unit, can be obtained as Ṽ da = (E2 - E1) μ12 Rda + (2 E3 - E1 - E2) 2 μ13 μ23 Rda2, where E1, E2, and E3 are adiabatic energies of the ground, charge-transfer, and bridge states, respectively, μij is the transition dipole moments between the states i and j, and Rda is the distance between the planes of donor and acceptor. In this expression based on the generalized Mulliken-Hush approach, the first term corresponds to the coupling derived within a two-state model, whereas the second term is the superexchange correction accounting for the bridge effect. The formula is extended to bridges consisting of several subunits. The influence of the donor-acceptor energy mismatch on the excess charge distribution, adiabatic dipole and transition moments, and electronic couplings is examined. A diagnostic is developed to determine whether the two-state approach can be applied. Based on numerical results, we showed that the superexchange correction considerably improves estimates of the donor-acceptor coupling derived within a two-state approach. In most cases when the two-state scheme fails, the formula gives reliable results which are in good agreement (within 5%) with the data of the three-state generalized Mulliken-Hush model

Robustness against large-scale failures in communications networks

This thesis studies robustness against large-scale failures in communications networks. If failures are isolated, they usually go unnoticed by users thanks to recovery mechanisms. However, such mechanisms are not effective against large-scale multiple failures. Large-scale failures may cause huge economic loss. A key requirement towards devising mechanisms to lessen their impact is the ability to evaluate network robustness. This thesis focuses on multilayer networks featuring separated control and data planes. The majority of the existing measures of robustness are unable to capture the true service degradation in such a setting, because they rely on purely topological features. One of the major contributions of this thesis is a new measure of functional robustness. The failure dynamics is modeled from the perspective of epidemic spreading, for which a new epidemic model is proposed. Another contribution is a taxonomy of multiple, large-scale failures, adapted to the needs and usage of the field of networking.