Quantitative prediction of charge mobilities of π-stacked systems by first-principles simulation

• DOI: 10.1038/nprot.2015.038
• Publication Date: 2015-03-26T16:19:39Z
• Authors: Wei-Qiao Deng; Lei Sun; Jin-Dou Huang; Shuo Chai; Shu-Hao Wen; Ke-Li Han
• Keywords: Models, Molecular; Naphthacenes; Semiconductors; Computer Simulation; DNA; Models, Theoretical; Crystallography, X-Ray; 01 natural sciences; 0104 chemical sciences

This protocol is intended to provide chemists and physicists with a tool for predicting the charge carrier mobilities of π-stacked systems such as organic semiconductors and the DNA double helix. An experimentally determined crystal structure is required as a starting point. The simulation involves the following operations: (i) searching the crystal structure; (ii) selecting molecular monomers and dimers from the crystal structure; (iii) using density function theory (DFT) calculations to determine electronic coupling for dimers; (iv) using DFT calculations to determine self-reorganization energy of monomers; and (v) using a numerical calculation to determine the charge carrier mobility. For a single crystal structure consisting of medium-sized molecules, this protocol can be completed in ∼4 h. We have selected two case studies (a rubrene crystal and a DNA segment) as examples of how this procedure can be used.