Srebro Monika, Autschbach Jochen
†Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260-3000, United States.
‡Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, 30-060 Krakow, Poland.
J Phys Chem Lett. 2012 Mar 1;3(5):576-81. doi: 10.1021/jz201685r. Epub 2012 Feb 14.
In the framework of determining system-specific long-range corrected density functionals, the question is addressed whether such functionals, tuned to satisfy the condition -ε(HOMO) = IP or other energetic criteria, provide accurate electron densities. A nonempirical physically motivated two-dimensional tuning of range-separated hybrid functionals is proposed and applied to the particularly challenging case of a molecular property that depends directly on the ground-state density: the copper electric field gradient (EFG) in CuCl. From a continuous range of functional parametrizations that closely satisfy -ε(HOMO) = IP and the correct asymptotic behavior of the potential, the one that best fulfills the straight-line behavior of E(N), the energy as a function of a fractional electron number N, was found to provide the most accurate electron density as evidenced by calculated EFGs. The functional also performs well for related Cu systems.
在确定特定体系的长程校正密度泛函的框架下，研究了这样一个问题：这些为满足-ε(HOMO)=IP或其他能量标准而调整的泛函是否能提供准确的电子密度。提出了一种基于物理动机的非经验二维范围分离混合泛函调谐方法，并将其应用于一个特别具有挑战性的分子性质案例，该性质直接依赖于基态密度：CuCl中的铜电场梯度（EFG）。从一系列紧密满足-ε(HOMO)=IP和势的正确渐近行为的泛函参数化中，发现最能满足E(N)（能量作为分数电子数N的函数）直线行为的那个参数化所提供的电子密度最准确，这一点由计算得到的EFG证明。该泛函在相关的铜体系中也表现良好。
