Combined DFT and Molecular Mechanics Modeling of the Adsorption of Semiconducting Molecules on an Ionic Substrate: PTCDA and CuPc on NaCl

Abstract

Experimental results suggest that molecular geometry and energies can be influenced by the presence of thin film substrates as well as surrounding molecules. It is imperative that computational models take this influence into account. The accurate computational modeling of these molecules is an efficient way of carrying out chemistry calculations and reinforcing experimental findings. In our study, density functional theory (DFT) and molecular mechanics (MM) are used to model the configurations of the organic semiconducting materials, 3,4,9,10-perylene tetracarboxylic dianhydride, C24H8O6 (PTCDA), and copper(II) phthalocyanine, C32H16CuN8 (CuPc), as adsorbed on single- and double-layer NaCl substrates of various dimensions and charge settings. After a geometry and charge optimization of the molecules using DFT, the molecular geometries are optimized under different environments using computational calculations with specific force-field settings in HyperChem Professional 8.0(TM) software using MM. Energies and geometries of the molecules are then recorded, and our data are compared to experimental results of similar systems. We find that, with the appropriate choice of substrate properties, the calculated molecular configurations directly reflect those found experimentally. Our results support the idea that this method of simulation can produce reliable models in the field of physical chemistry.