Theory of interfacial charge-transfer complex photophysics in π\pi-conjugated polymer-fullerene blends

We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component $\pi$-conjugated polymers, we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend, observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component $\pi$-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground-state charge transfer to the case of excited-state charge transfer.Comment: 9 pages, 8 figure

Correlated-electron description of the photophysics of thin films of π\pi-conjugated polymers

We extend Mulliken's theory of ground state charge transfer in a donor-acceptor complex to excited state charge transfer between pairs of identical $\pi$-conjugated oligomers, one of which is in the optically excited state and the other in the ground state, leading to the formation of a charge-transfer exciton. Within our theory, optical absorptions from the charge-transfer exciton should include a low energy intermolecular charge-transfer excitation, as well as distinct intramolecular excitations from both the neutral delocalized exciton component and the Coulombically bound polaron-pair component of the charge-transfer exciton. We report high order configuration-interaction calculations for pairs of oligomers of poly-paraphenylenevinylene (PPV) that go beyond our previous single configuration-interaction calculation and find all five excited state absorptions predicted using heuristic arguments based on the Mulliken concept. Our calculated excited state absorption spectrum exhibits strong qualitative agreement with the complete wavelength-dependent ultrafast photoinduced absorption in films of PPV derivatives, suggesting that a significant fraction of the photoinduced absorption here is from the charge-transfer exciton. We make detailed comparisons to experiments, and a testable experimental prediction

Ab initio parametrised model of strain-dependent solubility of H in alpha-iron

The calculated effects of interstitial hydrogen on the elastic properties of alpha-iron from our earlier work are used to describe the H interactions with homogeneous strain fields using ab initio methods. In particular we calculate the H solublility in Fe subject to hydrostatic, uniaxial, and shear strain. For comparison, these interactions are parametrised successfully using a simple model with parameters entirely derived from ab initio methods. The results are used to predict the solubility of H in spatially-varying elastic strain fields, representative of realistic dislocations outside their core. We find a strong directional dependence of the H-dislocation interaction, leading to strong attraction of H by the axial strain components of edge dislocations and by screw dislocations oriented along the critical slip direction. We further find a H concentration enhancement around dislocation cores, consistent with experimental observations.Comment: part 2/2 from splitting of 1009.3784 (first part was 1102.0187), minor changes from previous version