Dr Joseph Prentice

Abstract:

Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach.

Abstract:

Quantum embedding schemes have the potential to significantly reduce the computational cost of first principles calculations, whilst maintaining accuracy, particularly for calculations of electronic excitations in complex systems. In this work, I combine time-dependent embedded mean field theory (TD-EMFT) with linear-scaling density functional theory and implicit solvation models, extending previous work within the ONETEP code. This provides a way to perform multi-level calculations of electronic excitations on very large Systems, where long-range environmental effects, both quantum and classical in nature, are important. I demonstrate the power of this method by performing simulations on a variety of systems, including a molecular dimer, a chromophore in solution, and a doped molecular crystal. This work paves the way for high accuracy calculations to be performed on large-scale systems that were previously beyond the reach of quantum embedding schemes.

Abstract:

When calculating the optical absorption spectra of molecular crystals from first principles, the influence of the crystalline environment on the excitations is of significant importance. For such systems, however, methods to describe the excitations accurately can be computationally prohibitive due to the relatively large system sizes involved. In this work, we demonstrate a method that allows optical absorption spectra to be computed both efficiently and at high accuracy. Our approach is based on the spectral warping method successfully applied to molecules in solvent. It involves calculating the absorption spectrum of a supercell of the full molecular crystal using semi-local time-dependent density functional theory (TDDFT), before warping the spectrum using a transformation derived from smaller-scale semi-local and hybrid TDDFT calculations on isolated dimers. We demonstrate the power of this method on three polymorphs of the well-known color polymorphic compound ROY and find that it outperforms both small-scale hybrid TDDFT dimer calculations and large-scale semi-local TDDFT supercell calculations, when compared to the experiment.