Structure determination of chemisorbed chirality transfer complexes: Accelerated STM analysis and exchange-correlation functional sensitivity

Abstract

Linking STM images to atomic positions determined by DFT calculations is an important step in characterizing the intermolecular interactions at play in many surface processes including asymmetric hydrogenation on heterogeneous catalysts. An accelerated data extraction method is used to collect STM information on the geometry of complexes formed between the two substrates, 2,2,2-trifluoroacetophenone (TFAP) and 3,3,3-methyltrifluoropyruvate (MTFP), and the chiral modifier (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA) on Pt(111). We present new experimental data for complexes formed by MTFP and the (R)-NEA-1 conformer along with a new and enlarged set of reformulated STM data that extends what was reported in previously published studies of complexed MTFP and TFAP. Atomic geometries based on DFT calculations using PBE, M06-L, and optB88-vdW exchange-correlation functionals will also be presented. It will be shown that both substrates have well-defined complexation geometries when interacting with the modifier and that the relative complexation energies are not markedly sensitive to the functional employed.