To understand the influence of interchromophoric arrangements on photo-induced processes and optical properties of aggregates, it is fundamental to assess the contribution of local excitations [charge transfer (CT) and Frenkel (FE)] to exciton states. Here, we apply a general procedure to analyze the adiabatic exciton states derived from time-dependent density functional theory calculations, in terms of diabatic states chosen to coincide with local excitations within a restricted orbital space. In parallel, motivated by the need of cost-effective approaches to afford the study of larger aggregates, we propose to build a model Hamiltonian based on calculations carried out on dimers composing the aggregate. Both approaches are applied to study excitation energy profiles and CT character modulation induced by interchromophore rearrangements in perylene bisimide aggregates up to a tetramer. The dimer-based approach closely reproduces the results of full-aggregate calculations, and an analysis in terms of symmetry-adapted diabatic states discloses the effects of CT/FE interactions on the interchange of the H-/J-character for small longitudinal shifts of the chromophores.

Intermolecular interactions modulate the electro-optical properties of molecular materials and the nature of low-lying exciton states. Molecular materials composed by oligoacenes are extensively investigated for their semiconducting and optoelectronic properties. Here, we analyze the exciton states derived from time-dependent density functional theory (TDDFT) calculations for two oligoacene model aggregates: naphthalene and anthracene dimers. To unravel the role of inter-molecular interactions, a set of diabatic states is selected, chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space including two occupied and two unoccupied orbitals for each molecular monomer. We study energy profiles and disentangle inter-state couplings to disclose the (CT) character of singlet and triplet exciton states and assess the influence of inter-molecular orientation by displacing one molecule with respect to the other along the longitudinal translation coordinate. The analysis shows that (CT) contributions are relevant, although comparably less effective for triplet excitons, and induce a non-negligible mixed character to the low-lying exciton states for eclipsed monomers and for small translational displacements. Such (CT) contributions govern the L_a/L_b state inversion occurring for the low-lying singlet exciton states of naphthalene dimer and contribute to the switch from H- to J-aggregate type of the strongly allowed B_b transition of both oligoacene aggregates.

Using a new automatic fragmentation algorithm, deCOFpose , we elucidate how topologies and building blocks determine the band gaps of covalent organic frameworks.

Understanding structure-property relationships in ordered functional materials is essential for their rational design and optimisation. Fragment-based approaches relating materials’ properties to those of their building blocks (fragments) are intuitive to chemistry and have been successfully applied in the design of metal-organic frameworks (MOFs). However, covalent organic frameworks (COFs) are resistant to such in silico fragmentation due to their covalent bonds and ambiguous definitions of nodes and linkers. Here we introduce a new algorithm, deCOFpose, designed to systematically fragment COFs into building blocks according to chemically intuitive rules, enabling fragment-based structure-property analysis, and exemplify the latter for COFs band gaps. Our results reveal that the electronic features (e.g., energies of the frontier molecular orbitals) of the building blocks alone are insufficient to fully represent these materials, and the inclusion of their topological characteristics is required to engineer bespoke COFs with desired band structures.