No abstract

We report on quantum dynamical simulations of exciton diffusion in an oligo(para-phenylene vinylene) chain segment with 20 repeat units (OPV-20) at finite temperature, complementary to our recent study of the same system at T = 0 K [R. Binder and I. Burghardt, J. Chem. Phys. 152, 204120 (2020)]. Accurate quantum dynamical simulations are performed using the multi-layer multi-configuration time-dependent Hartree method as applied to a site-based Hamiltonian comprising 20 electronic states of Frenkel type and 460 vibrational modes, including site-local quinoid-distortion modes along with site-correlated bond-length alternation (BLA) modes, ring torsional modes, and an explicit harmonic-oscillator bath. A first-principles parameterized Frenkel–Holstein type Hamiltonian is employed, which accounts for correlations between the ring torsional modes and the anharmonically coupled BLA coordinates located at the same junction. Thermally induced fluctuations of the torsional modes are described by a stochastic mean-field approach, and their impact on the excitonic motion is characterized in terms of the exciton mean-squared displacement. A normal diffusion regime is observed under periodic boundary conditions, apart from transient localization features. Even though the polaronic exciton species are comparatively weakly bound, exciton diffusion is found to be a coherent—rather than hopping type—process, driven by the fluctuations of the soft torsional modes. Similar to the previous observations for oligothiophenes, the evolution for the most part exhibits a near-adiabatic dynamics of local exciton ground states (LEGSs) that adjust to the local conformational dynamics. However, a second mechanism, involving resonant transitions between neighboring LEGSs, gains importance at higher temperatures.

Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamical Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes.

The issue of the non-conservation of the oscillator strength in molecular aggregates is solved and several approximation schemes are validated.

Resonance energy transfer (RET) is a complex phenomenon where energy is transferred between two nonequivalent molecules. In the Förster picture, that applies to the weak coupling regime, RET occurs from the energy donor molecule in the relaxed excited state toward the acceptor, in an energy-conserving process. However, energy dissipation is crucial for a more general picture of RET that also applies to the strong coupling regime. Here we present a dynamical, nonadiabatic model for RET also accounting for energy relaxation. We exploit the essential state formalism to set up a model for the RET pair that yields an accurate picture of the relevant physics, accounting for just a few electronic states and a single coupled vibrational coordinate per molecule. Molecular vibrations are treated in a nonadiabatic approach, and energy dissipation is dealt within the Redfield formalism. The approach is first validated on an isolated dye, demonstrating that a very simple relaxation model, defined in terms of a single relaxation parameter, properly describes the different regimes of energy dissipation expected for a molecule, with a fast (fs time window) internal conversion to the lowest excited state and a slow relaxation toward the ground state (ns time window). The same approach is then applied to follow the real time dynamics of a RET pair. In line with the Förster model, in the weak coupling regime the internal conversion of the donor molecule is completed before energy transfer takes place. Our approach also applies to the strong coupling regime, where we observe ultrafast energy transfer occurring well before the internal relaxation of the energy donor is completed.