Accurate and Ultrafast Simulation of Molecular Recognition and Assembly on Metal Surfaces in Four Dimensions

Understanding
molecular interactions with metal surfaces in high
reliability is critical for the development of catalysts, sensors,
and therapeutics. Obtaining accurate experimental data for a wide
range of surfaces remains a critical bottleneck and quantum-mechanical
data remain speculative due to high uncertainties and limitations
in scale. We report molecular dynamics simulations of adsorption energies
and assembly of organic molecules on elemental metal surfaces using
the INTERFACE force field (IFF). The force field-based simulations
reach up to 8 times higher accuracy than density functional calculations
at a million-fold faster speed, as well as more than 1 order of magnitude
higher accuracy than other force fields relative to accurate measurements
by single-crystal adsorption calorimetry. Uncertainties of prior computational
methods are effectively reduced from on the order of 100% to less
than 10% and validated by experimental data from multiple sources.
Specifically, we describe the molecular interactions of benzene and
naphthalene with even and defective platinum surfaces across a wide
range of surface coverage in depth. We discuss molecular-scale influences
on the heat of adsorption and clarify the definition of surface coverage.
The methods can be applied to 18 metals to accurately predict binding
and assembly of organic molecules, ligands, electrolytes, biological
molecules, and gases without additional fit parameters.