An Effective Two-Orbital Quantum Chemical Model for Organic Photovoltaic Materials.

We present a coarse-grained quantum chemical model of organic photovoltaic materials, which is based on the classic idea that the main physical processes involve the electrons occupying the frontier orbitals (HOMO and LUMO) of each molecule or "site". This translates into an effective electronic Hamiltonian with two electrons and two orbitals per site. The on-site parameters (one- and two-electron integrals) can be rigorously related to the ionization energy, electron affinity, and singlet and triplet first excitation energies of that site. The intersite Hamiltonian parameters are introduced in a way that is consistent with classical electrostatics, and for the one-electron part, we use a simple approximation that could be refined using information from atomistic quantum chemical calculations. The model has been implemented within the GAMESS-US package. This allows the exploration of the physics of these materials using state-of-the art quantum chemical methods on relatively large systems (hundreds of electron-donor and electron-acceptor sites). To illustrate this point, we present ground- and excited-state calculations on dimers and two-dimensional arrays of sites using the Hartree-Fock, configuration interaction, and coupled-cluster methods. The calculations provide evidence for the possibility of low-energy, long-range electron transfer in donor-acceptor heterojunctions characterized by a moderate degree of disorder.