Read between the Molecules: Computational Insights into Organic Semiconductors

Abstract

The performance and key electronic properties of molecular organic semiconductors are dictated by the interplay between the chemistry of the molecular core and the intermolecular factors of which manipulation has inspired both experimentalists and theorists. This Perspective presents major computational challenges and modern methodological strategies to advance the field. The discussion ranges from insights and design principles at the quantum chemical level, in-depth atomistic modeling based on multiscale protocols, morphological prediction and characterization as well as energy-property maps involving data-driven analysis. A personal overview of the past achievements and future direction is also provided.

Recent developments in symmetry‐adapted perturbation theory

“…Noncovalent interactions are not only ubiquitous, but they are also absolutely necessary to describe many physical, chemical, and biochemical phenomena, ranging from thermodynamics of nonideal gases to spectroscopy and scattering cross sections of interstellar complexes to the performance and selectivity (including enantioselectivity) of molecular catalysts to the secondary, tertiary, and quaternary structure of proteins, the double‐helix structure of DNA, and the interaction between enzymes and their substrates (or inhibitors). Thus, theoretical and experimental investigations of noncovalent interactions are published in very large quantities, and various aspects of these interactions have been reviewed in this journal and elsewhere …”

Identifying high-mobility tetracene derivatives using a non-adiabatic molecular dynamics approach

“…35 Hopping models are based on the assumptions of weak intermolecular electronic coupling and charge transfer time scales much slower than the associated molecular motions, whereas band-like transfer models treat charge carriers as delocalized Bloch states in the low temperature limit. 36,37 Typical high mobility organic semiconductors cannot be safely modeled under ambient conditions utilizing either regime, since band transport models are compromised at room temperature and the requirements for thermally activated hopping can also be violated. [38][39][40] In order to overcome this obstacle, novel theories and methodologies have been developed, such as transient localization theory, 14,41 the time-dependent wavepacket diffusion method, 42 and the generalized Einstein relation approach.…”

Tuning Solid‐State Luminescence in Conjugated Organic Materials: Control of Excitonic and Excimeric Contributions through π Stacking and Halogen Bond Driven Self‐Assembly

“…The relative orientation of molecules and the resultant electronic/excitonic interactions are decisive in controlling the optical and electronic properties of the molecular materials . As nearest neighbour interactions contributes significantly towards the modification of the photophysical properties of the chromophores in the solid state, a first understanding can be based on a dimer model . In order to geometrically represent the dimers, the molecule is visualised in the xy plane with the long and short molecular axis oriented along the x and y axis, respectively.…”