Modeling Nonreactive Molecule-Surface Systems on Experimentally Relevant Time and Length Scales: Dynamics and...

We propose a computationally efficient strategy to accurately model nonreactive molecule-surface interactions that adapts density functional theory calculations with the Tkatchenko-Scheffler scheme for van der Waals interactions into a simple classical force field. The resulting force field requires just two adjustable parameters per atom type that are needed to capture short-range and polarization interactions. The developed strategy allows for classical molecular dynamics simulation of molecules on surfaces with the accuracy of high-level electronic structure methods but for system sizes (10³ to 10⁷ atoms) and timescales (picoseconds to microseconds) that go well beyond what can be achieved with first-principles methods. Parameters for H, sp² C, and O on Au(111) are developed and employed to atomistically model experiments that measure the conductance of a single polyfluorene on Au(111) as a continuous function of its length. The simulations qualitatively capture both the gross and fine features of the observed conductance decay during initial junction elongation and lead to a revised atomistic understanding of the experiment.