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A simple approach to hopping matrix elements between nearby molecules

Chemical Physics 2022-12-23 v1 Materials Science

Abstract

The hopping matrix element tt quantifies the quantum-mechanical coupling between frontier orbitals on a pair of nearby molecules. Convenient and generally applicable methods to determine tt from DFT calculations are lacking; tt can be obtained from coupling-induced energy splittings only if the interacting molecules are identical and symmetrically placed. We present a simple approach to determine tt from DFT results that relies on measuring hybridization, projecting hybridized pair orbitals onto constituent frontier orbitals of the interacting molecules, using spatially discretized wavefunctions (``cube files'') rather than analytical representations. We demonstrate the method by exploring how tt depends on the identity and relative placement of typical moieties found in semiconducting polymers.

Keywords

Cite

@article{arxiv.2212.11831,
  title  = {A simple approach to hopping matrix elements between nearby molecules},
  author = {Shane Donaher and Puja Agarwala and Scott T. Milner},
  journal= {arXiv preprint arXiv:2212.11831},
  year   = {2022}
}
R2 v1 2026-06-28T07:49:09.406Z