A New Anisotropic Charge-Equilibration Method for Self-Assembly of Organics on Metal Surface: d-Alaninol on Cu(100)

The supramolecular chemistry at surfaces has been extensively studied by quantum and classical computational models in order to simulate and reproduce the correct energetics and structures of adsorbed molecules on surfaces at various coverages. We have developed a classical tool able to sample the configuration space overcoming the topological constraints of the standard classical molecular dynamics. Our model is based on the charge equilibration procedure combined with an anisotropic pairwise atomic interaction where an angular dependence, with respect to the metal surface, is explicitly taken into account. The d-alaninol molecule has been chosen as a prototype of a flexible and multifunctional chemical compound which can form manifold complex configurations upon absorption on a metal surface. A detailed analysis of molecular structures and energetics of partial and full coverage has been carried out. The experimental STM image of the monolayer is correctly reproduced by our calculations, indicating that this new approach represents a step forward in the efficient simulation of complex molecular self-assembly.