arXiv subjects
Publications and source records attributed to V. A. Malyshev.
We show that optical properties of linear molecular aggregates undergo drastic changes when aggregates are deposited on a metal surface. The dipole-dipole interactions of monomers with their images can result in strong {re-structuring of both the exciton band and the absorption spectrum, depending on the arrangement of the monomer transition dipoles with respect to the surface.
The intrinsic double helix conformation of the DNA strands is known to be the key ingredient of control of the electric current through the DNA by the perpendicular (gate) electric field. We show theoretically that Bloch oscillations in the DNA are also strongly affected by such lateral field; the oscillation frequency splits into a manifold of several generally non-commensurate frequencies leading to a complicated pattern of the charge motion. The frequency of the oscillations falls in the THz domain, providing for a possibility to design a nano-scale source of THz radiation.
The study of energy harvesting in chain-like structures is important due to its relevance to a variety of interesting physical systems. Harvesting is understood as the combination of exciton transport through intra-band exciton relaxation (via scattering on phonon modes) and subsequent quenching by a trap. Previously, we have shown that in the low temperature limit different harvesting scenarios as a function of the applied bias strength (slope of the energy gradient towards the trap) are possible \cite{Vlaming07}. This paper generalizes the results for both homogeneous and disordered chains to nonzero temperatures. We show that thermal effects are appreciable only for low bias strengths, particularly so in disordered systems, and lead to faster harvesting.
We theoretically study the efficiency of energy harvesting in linear exciton chains with an energy bias, where the initial excitation is taking place at the high-energy end of the chain and the energy is harvested (trapped) at the other end. The efficiency is characterized by means of the average time for the exciton to be trapped after the initial excitation. The exciton transport is treated as the intraband energy relaxation over the states obtained by numerically diagonalizing the Frenkel Hamiltonian that corresponds to the biased chain. The relevant intraband scattering rates are obtained from a linear exciton-phonon interaction. Numerical solution of the Pauli master equation that describes the relaxation and trapping processes, reveals a complicated interplay of factors that determine the overall harvesting efficiency. Specifically, if the trapping step is slower than or comparable to the intraband relaxation, this efficiency shows a nonmonotonic dependence on the bias: it first increases when introducing a bias, reaches a maximum at an optimal bias value, and then decreases again because of dynamic (Bloch) localization of the exciton states. Effects of on-site (diagonal) disorder, leading to Anderson localization, are addressed as well.
We perform a theoretical study of the nonlinear optical response of an ultrathin film consisting of oriented linear aggregates. A single aggregate is described by a Frenkel exciton Hamiltonian with uncorrelated on-site disorder. The exciton wave functions and energies are found exactly by numerically diagonalizing the Hamiltonian. The principal restriction we impose is that only the optical transitions between the ground state and optically dominant states of the one-exciton manifold are considered, whereas transitions to other states, including those of higher exciton manifolds, are neglected. The optical dynamics of the system is treated within the framework of truncated optical Maxwell-Bloch equations in which the electric polarization is calculated by using a joint distribution of the transition frequency and the transition dipole moment of the optically dominant states. This function contains all the statistical information about these two quantities that govern the optical response, and is obtained numerically by sampling many disorder realizations. We derive a steady-state equation that establishes a relationship between the output and input intensities of the electric field and show that within a certain range of the parameter space this equation exhibits a three-valued solution for the output field. A time-domain analysis is employed to investigate the stability of different branches of the three-valued solutions and to get insight into switching times. We discuss the possibility to experimentally verify the bistable behavior.
We show that the third-order optical response of disordered linear J-aggregates can be calculated by considering only a limited number of transitions between (multi-) exciton states. We calculate the pump-probe absorption spectrum resulting from the truncated set of transitions and show that, apart from the blue wing of the induced absorption peak, it agrees well with the exact spectrum.
We argue that the time-resolved spectrum of selectively-excited resonance fluorescence at low temperature provides a tool for probing the quantum-mechanical level repulsion in the Lifshits tail of the electronic density of states in a wide variety of disordered materials. The technique, based on detecting the fast growth of a fluorescence peak that is red-shifted relative to the excitation frequency, is demonstrated explicitly by simulations on linear Frenkel exciton chains.
We study numerically the dynamics of a one-electron wave packet in a two-dimensional random lattice with long-range correlated diagonal disorder in the presence of a uniform electric field. The time-dependent Schrödinger equation is used for this purpose. We find that the wave packet displays Bloch-like oscillations associated with the appearance of a phase of delocalized states in the strong correlation regime. The amplitude of oscillations directly reflects the bandwidth of the phase and allows to measure it. The oscillations reveal two main frequencies whose values are determined by the structure of the underlying potential in the vicinity of the wave packet maximum.
We study numerically the linear optical response of a quasiparticle moving on a one-dimensional disordered lattice in the presence of a linear bias. The random site potential is assumed to be long-range-correlated with a power-law spectral density $S(k) \sim 1/k^α$, $α> 0$. This type of correlations results in a phase of extended states at the band center, provided $α$ is larger than a critical value $α_c$ [F. A. B. F. de Moura and M. L. Lyra, Phys. Rev. Lett. \textbf{81}, 3735 (1998)]. The width of the delocalized phase can be tested by applying an external electric field: Bloch-like oscillations of a quasiparticle wave packet are governed by the two mobility edges, playing now the role of band edges [F. Dom\'ınguez-Adame \emph{et al.}, Phys. Rev. Lett. \textbf{91}, 197402 (2003)]. We demonstrate that the frequency-domain counterpart of these oscillations, the so-called Wannier-Stark ladder, also arises in this system. When the phase of extended states emerges in the system, this ladder turns out to be a comb of doublets, for some range of disorder strength and bias. Linear optical absorption provides a tool to detect this level structure.
We theoretically analyze the excitation energy transfer between two closely spaced linear molecular J-aggregates, whose excited states are Frenkel excitons. The aggregate with the higher (lower) exciton band edge energy is considered as the donor (acceptor). The celebrated theory of Förster resonance energy transfer (FRET), which relates the transfer rate to the overlap integral of optical spectra, fails in this situation. We point out that in addition to the well-known fact that the point-dipole approximation breaks down (enabling energy transfer between optically forbidden states), also the perturbative treatment of the electronic interactions between donor and acceptor system, which underlies the Förster approach, in general loses its validity due to overlap of the exciton bands. We therefore propose a nonperturbative method, in which donor and acceptor bands are mixed and the energy transfer is described in terms of a phonon-assisted energy relaxation process between the two new (renormalized) bands. The validity of the conventional perturbative approach is investigated by comparing to the nonperturbative one; in general this validity improves for lower temperature and larger distances (weaker interactions) between the aggregates. We also demonstrate that the interference between intraband relaxation and energy transfer renders the proper definition of the transfer rate and its evaluation from experiment a complicated issue, which involves the initial excitation condition.
Using a model of Frenkel excitons coupled to a bath of acoustic phonons in the host medium, we study the temperature dependence of the dephasing rates and homogeneous line width in linear molecular aggregates. The model includes localization by disorder and predicts a power-law thermal scaling of the effective homogeneous line width. The theory gives excellent agreement with temperature dependent absorption and hole-burning experiments on aggregates of the dye pseudoisocyanine.
We study the temperature-dependent dephasing rate of excitons in chains of chromophores, accounting for scattering on static disorder as well as acoustic phonons in the host matrix. From this we find a powerlaw temperature dependence of the absorption line width, in excellent quantitative agreement with experiments on dye aggregates. We also propose a relation between the line width and the exciton coherence length imposed by the phonons. The results indicate that the much debated steep rise of the fluorescence lifetime of pseudo-isocyanine aggregates above 40 K results from the fact that this coherence length drops below the localization length imposed by static disorder.
We theoretically study the temperature dependence of the J-band width in disordered linear molecular aggregates, caused by dephasing of the exciton states due to scattering on vibrations of the host matrix. In particular, we consider inelastic one- and two-phonon scattering between different exciton states (energy-relaxation-induced dephasing), as well as elastic two-phonon scattering of the excitons (pure dephasing). The exciton states follow from numerical diagonalization of a Frenkel Hamiltonian with diagonal disorder; the scattering rates between them are obtained using the Fermi Golden Rule. A Debye-like model for the one- and two-phonon spectral densities is used in the calculations. We find that, owing to the disorder, the dephasing rates of the individual exciton states are distributed over a wide range of values. We also demonstrate that the dominant channel of two-phonon scattering is not the elastic one, as is often tacitly assumed, but rather comes from a similar two-phonon inelastic scattering process. In order to study the temperature dependence of the J-band width, we simulate the absorption spectrum, accounting for the dephasing induced broadening of the exciton states. We find a power-law (T^p) temperature scaling of the effective homogeneous width, with an exponent p that depends on the shape of the spectral density of host vibrations. In particular, for a Debye model of vibrations, we find p ~ 4, which is in good agreement with experimental data on J-aggregates of pseudoisocyanine [J. Phys. Chem. A 101, 7977 (1997)].
We perform both analytical and numerical studies of the one-dimensional tight-binding Hamiltonian with stochastic uncorrelated on-site energies and non-fluctuating long-range hopping integrals . It was argued recently [A. Rodriguez at al., J. Phys. A: Math. Gen. 33, L161 (2000)] that this model reveals a localization-delocalization transition with respect to the disorder magnitude provided . The transition occurs at one of the band edges (the upper one for and the lower one for). The states at the other band edge are always localized, which hints on the existence of a single mobility edge. We analyze the mobility edge and show that, although the number of delocalized states tends to infinity, they form a set of null measure in the thermodynamic limit, i.e. the mobility edge tends to the band edge. The critical magnitude of disorder for the band edge states is computed versus the interaction exponent by making use of the conjecture on the universality of the normalized participation number distribution at transition.
We report on an anomalous behavior of the absorption spectrum in a one-dimensional lattice with long-range-correlated diagonal disorder with a power-like spectrum in the form S(k) ~ 1/k^A. These type of correlations give rise to a phase of extended states at the band center, provided A is larger than a critical value A_c. We show that for A < A_c the absorption spectrum is single-peaked, while an additional peak arises when A > A_c, signalling the occurrence of the Anderson transition. The peak is located slightly below the low-energy mobility edge, providing a unique spectroscopic tool to monitor the latter. We present qualitative arguments explaining this anomaly.
We consider a two-parameter one-dimensional Hamiltonian with uncorrelated diagonal disorder and {\it non-random} long-range inter-site interaction $J_{mn}=J/|m-n|^μ$. The model is critical at $1<μ<3/2$ and reveals the localization-delocalization transition with respect to the disorder magnitude. To detect the transition we analyze level and wave function statistics. It is demonstrated also that in the marginal case ($μ= 3/2$) all states are localized.
We study the dynamics of an electron subjected to a static uniform electric field within a one-dimensional tight-binding model with a slowly varying aperiodic potential. The unbiased model is known to support phases of localized and extended one-electron states separated by two mobility edges. We show that the electric field promotes sustained Bloch oscillations of an initial Gaussian wave packet whose amplitude reflects the band width of extended states. The frequency of these oscillations exhibit unique features, such as a sensitivity to the initial wave packet position and a multimode structure for weak fields, originating from the characteristics of the underlying aperiodic potential.
We study the dynamics of an electron subjected to a uniform electric field within a tight-binding model with long-range-correlated diagonal disorder. The random distribution of site energies is assumed to have a power spectrum $S(k) \sim 1/k^α$ with $α> 0$. Moura and Lyra [Phys. Rev. Lett. {\bf 81}, 3735 (1998)] predicted that this model supports a phase of delocalized states at the band center, separated from localized states by two mobility edges, provided $α> 2$. We find clear signatures of Bloch-like oscillations of an initial Gaussian wave packet between the two mobility edges and determine the bandwidth of extended states, in perfect agreement with the zero-field prediction.