Comparative study of microscopic charge dynamics in crystalline acceptor-substituted oligothiophenes.

By performing microscopic charge transport simulations for a set of crystalline dicyanovinyl-substituted oligothiophenes, we find that the internal acceptor-donor-acceptor molecular architecture combined with thermal fluctuations of dihedral angles results in large variations of local electric fields, substantial energetic disorder, and pronounced Poole-Frenkel behavior, which is unexpected for crystalline compounds. We show that the presence of static molecular dipoles causes large energetic disorder, which is mostly reduced not by compensation of dipole moments in a unit cell but by molecular polarizabilities. In addition, the presence of a well-defined π-stacking direction with strong electronic couplings and short intermolecular distances turns out to be disadvantageous for efficient charge transport since it inhibits other transport directions and is prone to charge trapping.

Microscopic Simulations of Charge Transport in Disordered Organic Semiconductors.

Charge carrier dynamics in an organic semiconductor can often be described in terms of charge hopping between localized states. The hopping rates depend on electronic coupling elements, reorganization energies, and driving forces, which vary as a function of position and orientation of the molecules. The exact evaluation of these contributions in a molecular assembly is computationally prohibitive. Various, often semiempirical, approximations are employed instead. In this work, we review some of these approaches and introduce a software toolkit which implements them. The purpose of the toolkit is to simplify the workflow for charge transport simulations, provide a uniform error control for the methods and a flexible platform for their development, and eventually allow in silico prescreening of organic semiconductors for specific applications. All implemented methods are illustrated by studying charge transport in amorphous films of tris-(8-hydroxyquinoline)aluminum, a common organic semiconductor.

Simulation of vapor-liquid coexistence in finite volumes: a method to compute the surface free energy of droplets.

When a fluid at a constant density rho in between the densities of coexisting vapor (rhov) and liquid (rhol) at temperatures below criticality is studied in a (cubic) box of finite linear dimension L , phase separation occurs in this finite volume, provided L is large enough. For a range of densities, one can observe a liquid droplet (at density rhol' slightly exceeding rhol) coexisting in stable thermal equilibrium with surrounding vapor (with density rhov'>rhov, so in the thermodynamic limit such a vapor would be supersaturated). We show, via Monte Carlo simulations of a Lennard-Jones model of a fluid and based on a phenomenological thermodynamic analysis, that via recording the chemical potential micro as function of rho, one can obtain precise estimates of the droplet surface free energy for a wide range of droplet radii. We also show that the deviations of this surface free energy from the prediction based on the "capillarity approximation" of classical nucleation theory (i.e., using the interfacial free energy of a flat liquid-vapor interface for the surface free energy of a droplet irrespective of its radius) are rather small. We also study carefully the limitation of the present method due to the "droplet evaporation/condensation transition" occurring for small volumes and demonstrate that very good equilibrium is achieved in our study, by showing that the radial profile of the local chemical potential from the droplet center to the outside is perfectly flat.