Characterization of enantiospecific chemisorption on chiral Cu surfaces vicinal to Cu(111) and Cu(100) using density functional theory

Abstract

Surfaces of simple fcc metals such as Cu with nonzero and unequal Miller indices are intrinsically chiral. Density functional theory (DFT) calculations are a useful way to study the enantiospecific adsorption of small chiral molecules on these chiral metal surfaces. We report DFT calculations of seven chiral molecules on several structurally distinct chiral Cu surfaces. These surfaces include two surfaces with (111)-oriented terraces and one with (100)-oriented terraces. Calculations are also described on a surface that was modified to mimic the surface structures that typically appear on real metal surfaces following thermally driven fluctuations in step edges. Our results provide initial information on how variation in the surface structure of intrinsically chiral metal surfaces can affect the enantiospecific adsorption of small molecules on these surfaces.

The Study of Chiral Adsorption Systems Using Synchrotron-Based Structural and Spectroscopic Techniques: Stereospecific Adsorption of Serine on Au-Modified Chiral Cu{531} Surfaces

“…More detailed crystallographic information about the number and nature of enantiospecific interactions between chiral adsorbates and a metal surface emerged over the last few years, both from theory and experiment [19][20][21][22][23][24][25][26][27]. The first combination of experimental and theoretical work in this context was a combined DFT and photoelectron diffraction study of enantioselective effects in the adsorption geometry of cysteine on Au{17 11 9} by Greber et al [22].…”

The Importance of Attractive Three-Point Interaction in Enantioselective Surface Chemistry: Stereospecific Adsorption of Serine on the Intrinsically Chiral Cu{531} Surface

“…More detailed information about the number and nature of interactions with the metal surface only emerged over the last few years, both from theory and experiment. [9][10][11][12][13][14] So far, however, it was not possible to identify the type of bonds necessary to induce enantioselectivity in such adsorption systems.…”

Ionic Liquid Chiral Resolution: Methyl 2-Ammonium Chloride Propanoate on Al(854)SSurface

“…This implies a difference in adsorption energy of 0.08 eV -7.9 kJ mol -1 -, in the range of other reported energy differences on enantioselective adsorption processes. [40][41][42] Assuming a steady-state surface situation at 300 K, a Maxwell-Boltzmann distribution implies a ~96% ee of R-enantiomer. In a very straightforward way, and because of the specular symmetry, the same ee is expected for S-enantiomer on the Al(854) R surface.…”