Controlling preferential motion of chiral molecular walkers at a surface

Abbasi-Pérez, David and Hongqian, Sang and Pérez-García, Lluïsa and Floris, Andrea and Amabilino, David B and Raval, Rasmita and Recio, J. Manuel and Kantorovich, Lev (2019) Controlling preferential motion of chiral molecular walkers at a surface. Chemical Science, 23 . pp. 5864-5874. ISSN 2041-6520

Full content URL: http://doi.org/10.1039/C9SC01135H

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Abstract

Molecular walkers standing on two or more “feet” on an anisotropic periodic potential of a crystal surface may perform a one-dimensional Brownian motion at the surface-vacuum interface along a particular direction in which their mobility is the largest. In thermal equilibrium the molecules move with equal probabilities both ways along this direction, as expected from the detailed balance principle, well-known in chemical reactivity and in the theory of molecular motors. For molecules that possess an asymmetric potential energy surface (PES), we propose a generic method based on the application of a time-periodic external stimulus that would enable the molecules to move preferentially in a single direction thereby performing as Brownian ratchets. To illustrate this method, we consider a prototypical synthetic chiral molecular walker, the 1,3-bis(imidazol-1-ylmethyl)-5(1-phenylethyl)benzene, diffusing on the anisotropic Cu(110) surface along the Cu rows. As unveiled by our kinetic Monte Carlo simulations based on the rates calculated using ab initio density functional theory, this molecule moves to the nearest equivalent lattice site via the so-called inchworm mechanism in which it steps first with the rear and then with the front foot. As a result, the molecule diffuses via a two-step mechanism, and due to its inherent asymmetry, the corresponding PES is also spatially asymmetric. Taking advantage of this fact, we show how the external stimulus can be tuned to separate molecules of different chirality, orientation and conformation. The consequences of these findings for molecular machines and the separation of enantiomers are also discussed.

Keywords:nudged elastic band, Density functional theory, Chirality, rate equations
Subjects:F Physical Sciences > F170 Physical Chemistry
F Physical Sciences > F343 Computational Physics
F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:35980
Deposited On:17 May 2019 08:35

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