Analysis of nonlocal electronic correlation on enantioselective adsorption

van der Waals (vdW) interactions play a central role in the structure, stability, and function of a wide variety of systems, ranging from microscopic, few-molecule systems such as the benzene dimer, to mesoscopic scales as seen in surfaces and clusters. They are responsible for many natural processes, and thus, an accurate description of vdW forces is essential for improving our understanding of various biological, chemical, and physical phenomena^[1]. In this talk, we present our findings on the role of non-local vdW interactions on chirality; more specifically, in the enantioselective adsorption and debromination of the 10,10’-dibromo-9,9’-bianthracene (DBBA) and 9-Phenanthracenylboronic acid (9-PBA) molecules, as catalyzed by chiral surfaces of the palladium-gallium (PdGa) intermetallic compound^[2]. After a brief recapitulation on the framework of density-functional theory (DFT) with dispersion corrections^[3], we discuss its principle shortcomings within the context of many-body perturbation theory, and how our current calculations address and rectify these faults via higher- order treatments of the exchange integrals. We then present several figures of interest – adsorption configurations before and after geometry optimizations, charge localization plots of adsorption, molecular energetics obtained via ab-initio molecular dynamics, as well as the location of the transition state from metadynamics – and explore effects of both vdW interactions and the nonlocal exchange term via inclusion of hybrid functionals^[4]. In doing so, we provide the foundations for further study of non-local electronic correlation in chirality.