Long-range repulsive interaction between TTF molecules on a metal surface induced by charge transfer

TL;DR

This study reveals that TTF molecules on Au(111) surfaces exhibit long-range electrostatic repulsive interactions caused by charge transfer, influencing their self-assembly and spacing.

Contribution

It demonstrates that charge transfer induces electrostatic repulsion between TTF molecules, explaining their unique superlattice formation on metal surfaces.

Findings

Long-range repulsive electrostatic interactions between TTF molecules.

Charge transfer from TTF to Au(111) causes molecular repulsion.

Molecular spacing depends on coverage and charge transfer effects.

Abstract

The low-coverage adsorption of a molecular electron donor, tetrathiafulvalene, on Au(111) is characterized by the spontaneous formation of superlattice of monomers, whose spacing exceeds the equilibrium distance of non-covalent interactions and depends on coverage. The origin of this peculiar growth mode is due to a long-range repulsive interaction between molecules. The analysis of molecular-pair distributions obtained by scanning tunneling microscopy measurements permits us to determine that the nature of TTF intermolecular interactions on Au (111) is electrostatic. A repulsion between molecules is caused by the accumulation of charge due to electron donation into the metal surface, as pictured through density functional theory calculations.