Influence of static disorder and polaronic band formation on interfacial electron transfer in organic photovoltaic devices

Understanding the interfacial charge-separation mechanism in organic photovoltaics requires, due to its high level of complexity, bridging between chemistry and physics. To elucidate the charge separation mechanism, we present a fully quantum dynamical simulation of a generic one-dimensional Hamiltonian, which physical parameters model prototypical PCBM or $\text{C}_{60}$ acceptor systems. We then provide microscopic evidence of the influence random static and dynamic potentials have on the interfacial charge-injection rate. In particular, we unveil that dynamic potentials, due to strong electron-vibration interactions, can lead to the formation of polaronic bands. Such dynamical potentials, when compared to random static potentials, can provide the main detrimental influence on the efficiency of the process of interfacial charge-separation

Aspects of Discrete Breathers and New Directions

We describe results concerning the existence proofs of Discrete Breathers (DBs) in the two classes of dynamical systems with optical linear phonons and with acoustic linear phonons. A standard approach is by continuation of DBs from an anticontinuous limit. A new approach, which is purely variational, is presented. We also review some numerical results on intraband DBs in random nonlinear systems. Some non-conventional physical applications of DBs are suggested. One of them is understanding slow relaxation properties of glassy materials. Another one concerns energy focusing and transport in biomolecules by targeted energy transfer of DBs. A similar theory could be used for describing targeted charge transfer of nonlinear electrons (polarons) and, more generally, for targeted transfer of several excitations (e.g. Davydov soliton).Comment: to appear in the Proceedings of NATO Advanced Research Workshop "Nonlinearity and Disorder: Theory and Applications", Tashkent,Uzbekistan,October 1-6, 200

Harmonic Solid Theory of Photoluminescence in the High Field Two-Dimensional Wigner Crystal

Motivated by recent experiments on radiative recombination of two-dimensional electrons in acceptor doped GaAs-AlGaAs heterojunctions as well as the success of a harmonic solid model in describing tunneling between two-dimensional electron systems, we calculate within the harmonic approximation and the time dependent perturbation theory the line shape of the photoluminescence spectrum corresponding to the recombination of an electron with a hole bound to an acceptor atom. The recombination process is modeled as a sudden perturbation of the Hamiltonian for the in-plane degrees of freedom of the electron. We include in the perturbation, in addition to changes in the equilibrium positions of electrons, changes in the curvatures of the harmonically approximated potential. The computed spectra have line shapes similar to that seen in a recent experiment. The spectral width, however, is roughly a factor of 3 smaller than that seen in experiment if one assumes a perfect Wigner crystal for the initial state state of the system, whereas a simple random disorder model yields a width a factor of 3 too large. We speculate on the possible mechanisms that may lead to better quantitative agreement with experiment.Comment: 22 pages, RevTex, 8 figures. Submitted to the Physical Review

Tight-binding approximation for semi-infinite solids. Application of a transform method and of delta function normalization

A transform method for treating semi‐infinite solids in the tight‐binding (TB) approximation is introduced. The difference equations for the TB orbital coefficients are converted, thereby, to convenient algebraic equations. For this purpose, a Dirac delta function normalization for the wave function is also introduced, instead of the usual box one. Single and coupled bands are treated, and the methods are applied elsewhere to electron transfer problems at interfaces

London force and energy transportation between interfacial surfaces

With appropriately selected optical frequencies, pulses of radiation propagating through a system of chemically distinct and organized components can produce areas of spatially selective excitation. This paper focuses on a system in which there are two absorptive components, each one represented by surface adsorbates arrayed on a pair of juxtaposed interfaces. The adsorbates are chosen to be chemically distinct from the material of the underlying surface. On promotion of any adsorbate molecule to an electronic excited state, its local electronic environment is duly modified, and its London interaction with nearest neighbor molecules becomes accommodated to the new potential energy landscape. If the absorbed energy then transfers to a neighboring adsorbate of another species, so that the latter acquires the excitation, the local electronic environment changes and compensating motion can be expected to occur. Physically, this is achieved through a mechanism of photon absorption and emission by molecular pairs, and by the engagement of resonance transfer of energy between them. This paper presents a detailed analysis of the possibility of optically effecting such modifications to the London force between neutral adsorbates, based on quantum electrodynamics (QED). Thus, a precise link is established between the transfer of excitation and ensuing mechanical effects

On the Complexity of the Word Problem for Automaton Semigroups and Automaton Groups

In this paper, we study the word problem for automaton semigroups and automaton groups from a complexity point of view. As an intermediate concept between automaton semigroups and automaton groups, we introduce automaton-inverse semigroups, which are generated by partial, yet invertible automata. We show that there is an automaton-inverse semigroup and, thus, an automaton semigroup with a PSPACE-complete word problem. We also show that there is an automaton group for which the word problem with a single rational constraint is PSPACE-complete. Additionally, we provide simpler constructions for the uniform word problems of these classes. For the uniform word problem for automaton groups (without rational constraints), we show NL-hardness. Finally, we investigate a question asked by Cain about a better upper bound for the length of a word on which two distinct elements of an automaton semigroup must act differently