Kim Min-Cheol, Park Hansol, Son Suyeon, Sim Eunji, Burke Kieron
Department of Chemistry and Institute of Nano-Bio Molecular Assemblies, Yonsei University , 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, Korea.
Department of Chemistry, University of California , 1102 Natural Sciences 2, Irvine, California 92697, United States.
J Phys Chem Lett. 2015 Oct 1;6(19):3802-7. doi: 10.1021/acs.jpclett.5b01724. Epub 2015 Sep 10.
Density-corrected DFT is a method that cures several failures of self-consistent semilocal DFT calculations by using a more accurate density instead. A novel procedure employs the Hartree-Fock density to bonds that are more severely stretched than ever before. This substantially increases the range of accurate potential energy surfaces obtainable from semilocal DFT for many heteronuclear molecules. We show that this works for both neutral and charged molecules. We explain why and explore more difficult cases, for example, CH(+), where density-corrected DFT results are even better than sophisticated methods like CCSD. We give a simple criterion for when DC-DFT should be more accurate than self-consistent DFT that can be applied for most cases.
密度校正密度泛函理论（DFT）是一种通过使用更精确的密度来解决自洽半局域DFT计算中若干缺陷的方法。一种新方法将Hartree-Fock密度应用于比以往拉伸程度更大的化学键。这极大地扩展了通过半局域DFT可获得的许多异核分子精确势能面的范围。我们表明，这对中性分子和带电分子均有效。我们解释了其原理，并探讨了更具挑战性的情况，例如CH⁺，在这种情况下密度校正DFT的结果甚至优于诸如耦合簇单双激发（CCSD）等复杂方法。我们给出了一个简单的判据，用于判断在何种情况下密度校正DFT比自洽DFT更精确，该判据适用于大多数情况。
