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

PT−{\cal PT}-Symmetric Dimers with Time-Periodic Gain/Loss Function

${\mathcal PT}-$symmetric dimers with a time-periodic gain/loss function in a balanced configuration where the amount of gain equals that of loss are investigated analytically and numerically. Two prototypical dimers in the linear regime are investigated: a system of coupled classical oscillators, and a Schr\"{o}dinger dimer representing the coupling of field amplitudes; each system representing a wide class of physical models. Through a thorough analysis of their stability behaviour, we find that turning on the coupling parameter in the classical dimer system, leads initially to decreased stability but then to re-entrant transitions from the exact to the broken ${\mathcal PT}-$phase and vice versa, as it is increased beyond a critical value. On the other hand, the Schr\"{o}dinger dimer behaves more like a single oscillator with time-periodic gain/loss. In addition, we are able to identify the conditions under which the behaviour of the two dimer systems coincides and/or reduces to that of a single oscillator.Comment: 9 pages, 9 figures, META14 Conference, subm. Special Issue Appl. Phys.