Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
J Chem Phys. 2010 Nov 7;133(17):174115. doi: 10.1063/1.3503656.
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.
力匹配方法通过设计补充势来改进密度泛函理论（DFT），以捕捉 DFT 泛函与高质量 Hartree-Fock 后方法之间原子力的差异。补充势具有设计用于纠正色散和氢键相互作用的二体项。该势还具有改善分子内势能表面描述的单体项。我们的程序通过为水提供对 Becke-Lee-Yang-Parr 交换相关泛函的修正来进行测试，发现它的性能明显优于标准 DFT-D 方法，为相对团簇能量、原子力和分子结构提供了 QCISD 质量预测。结果发现，简单的 Lennard-Jones 项可以很好地纠正范德华相互作用，并可能为交换排斥提供修正。单体修正虽然对改善相对团簇能量的贡献很小，但大大降低了所研究体系中结合能和原子力的误差。
