Correcting for dispersion interaction and beyond in density functional theory through force matching

The force matching method is used to improve density functional theory (DFT) by designing a supplemental potential to capture the difference in atomic forces between a DFT functional and a high-quality post Hartree-Fock method. The supplemental potential has two-body terms designed to correct for dispersion and hydrogen bond interactions. The potential also has one-body terms to improve the description of the intramolecular potential energy surface. Our procedure is tested by providing corrections to the Becke-Lee-Yang-Parr exchange-correlation functional for water and is found to perform significantly better than the standard DFT-D approach, giving QCISD quality predictions for relative cluster energies, atomic forces, and molecular structures. It is found that a simple Lennard-Jones term does a good job at correcting for van der Waals interactions and possibly also providing corrections to exchange repulsion. The one-body corrections, while contributing only slightly to improving relative cluster energies, significantly reduce the errors in binding energies and atomic forces for the systems studied. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3503656]