March 2014   (Technical report   )

Walking-like diffusion of two-footed asymmetric aromatic adsorbates on Pt(111)

Guillaume Goubert, Anton Rasmussen, Yi Dong, Michael N. Groves, Peter McBreen

We present a combined density functional theory (DFT) and scanning tunneling microscopy (STM) investigation of the adsorption and diffusion of non-interacting 2,2,2-trifluoroacetophenone (TFAP) and (R)-(+)-1-(1-naphthyl)ethylamine ((R)-NEA) on the Pt(111) surface. The two adsorbates are prochiral and chiral, respectively, and their surface diffusion is of specific interest in relation to chirality transfer from chiral modifiers to prochiral reactants in Orito-type hydrogenation on metal catalysts. Using a van der Waals-DFT description, the two adsorbates are shown to bind strongly to the surface through the aromatic groups and their respective side groups with carbonyl and amine functions. Adsorption energies were calculated for twelve different (R)-NEA adsorption conformers. A naming convention is introduced to describe the different conformers, and the two most stable ones are labeled (R)-NEA-1 and (R)-NEA-2. Diffusion of both adsorbates is calculated to proceed in a “walking” manner, moving either the aromatic group or the substituent group. For TFAP a diffusion barrier of 0.66 eV is calculated while 0.74–0.89 eV barriers are found for the two adsorption conformers of (R)-NEA. In agreement with the computed results, the room temperature STM study shows rapid diffusion of TFAP and significantly slower diffusion of (R)-NEA. Whereas TFAP monomers are rarely imaged at room temperature, consistent with rapid diffusion, time-lapsed images of (R)-NEA show limited molecular motion in localized regions of the surface. Furthermore, the motion of (R)-NEA is strongly conformation dependent. (R)-NEA-1 displays a much greater propensity to undergo rotational motion. The STM data for (R)-NEA are compared with DFT calculated energy barriers for translation and rotation. The possible implications of the experimental and calculated data for a role for induced fit stereodirection by (R)-NEA/Pt(111) are commented on.

http://www.sciencedirect.com/science/article/pii/S0039602814000879#