Exciton scattering on symmetric branching centers in conjugated molecules.

The capability of the exciton scattering approach, an efficient methodology for excited states in branched conjugated molecules, is extended to include symmetric triple and quadruple joints that connect linear segments on the basis of the phenylacetylene backbone. The obtained scattering matrices that characterize these vertices are used in application of our approach to several test structures, where we find excellent agreement with the transition energies computed by the reference quantum chemistry. We introduce topological charges, associated with the scattering matrices, which help to formulate useful relations between the number of excitations in the exciton band and the number of repeat units.

Exciton scattering approach for branched conjugated molecules and complexes. IV. Transition dipoles and optical spectra.

The electronic excitation energies and transition dipole moments are the essential ingredients to compute an optical spectrum of any molecular system. Here we extend the exciton scattering (ES) approach, originally developed for computing excitation energies in branched conjugated molecules, to the calculation of the transition dipole moments. The ES parameters that characterize contributions of molecular building blocks to the total transition dipole can be extracted from the quantum-chemical calculations of the excited states in simple molecular fragments.

Transition times in the low-noise limit of stochastic dynamics.

We study the transition time distribution for a particle moving between two wells of a multidimensional potential in the low-noise limit of overdamped Langevin dynamics. Possible transition paths are restricted to a thin tube surrounding the most probable trajectory. We demonstrate that finding the transition time distribution reduces to a one-dimensional problem.

Exciton scattering approach for branched conjugated molecules and complexes. III. Applications.

The exciton scattering (ES) approach is an efficient tool to calculate the excited states electronic structure in large branched polymeric molecules. Using the previously extracted parameters, we apply the ES approach to a number of phenylacetylene-based test molecules. Comparison of ES predictions with direct quantum chemistry results for the excitation energies shows an agreement within several meV.

Exciton scattering approach for branched conjugated molecules and complexes. I. Formalism.

We develop a formalism for the exciton scattering (ES) approach to calculation of the excited state electronic structure of branched conjugated polymers with insignificant numerical expense. The ES approach attributes electronic excitations in quasi-one-dimensional molecules to standing waves formed by the scattering of quantum quasiparticles. We derive the phenomenology from the microscopic description in terms of many-electron excitations.

Classical nonlinear response of a chaotic system. II. Langevin dynamics and spectral decomposition.

The spectrum of a strongly chaotic system consists of discrete complex Ruelle-Pollicott (RP) resonances. We interpret the RP resonances as eigenstates and eigenvalues of the Fokker-Planck operator obtained by adding an infinitesimal diffusion term to the first-order Liouville operator. We demonstrate how the deterministic expression for the linear response is reproduced in the limit of vanishing noise.

Classical nonlinear response of a chaotic system. I. Collective resonances.

We develop a general semiquantitative picture of nonlinear classical response in strongly chaotic systems. In contrast to behavior in integrable or almost integrable systems, the nonlinear classical response in chaotic systems vanishes at long times. The exponential decay of the response functions in the case of strong chaos is attributed to both exponentially decaying and growing elements in the stability matrices.

Multiscale modeling of electronic excitations in branched conjugated molecules using an exciton scattering approach.

The exciton scattering (ES) approach attributes excited electronic states in quasi-1D branched polymer molecules to standing waves of quantum quasiparticles (excitons) scattered at the molecular vertices. We extract their dispersion and frequency-dependent scattering matrices at termini, ortho, and meta joints for pi-conjugated phenylacetylene-based molecules from atomistic time-dependent density-functional theory (TD DFT) calculations. This allows electronic spectra for any structure of arbitrary size within the considered molecular family to be obtained with negligible numerical effort.

Collective oscillations in the classical nonlinear response of a chaotic system.

We establish a general semiquantitative phase-space picture of the classical nonlinear response in a strongly chaotic system. As opposed to the case of stable dynamics, the response functions decay exponentially at long times. Damped oscillations in response functions are attributed to collective resonances which do not correspond to any periodic classical motions.