密度泛函理论
轨道自由密度泛函理论
统计物理学
计算
工作(物理)
含时密度泛函理论
计算化学
实验数据
混合功能
化学
热力学
物理
数学
算法
统计
摘要
Kohn-Sham density-functional theory (DFT), the predominant framework for electronic structure computations in chemistry today, has undergone considerable evolution in the past few decades. The earliest DFT approximations were based on uniform electron gas models completely free of empirical parameters. Tremendous improvements were made by incorporating density gradients and a small number of parameters, typically one or two, obtained from fits to atomic data. Incorporation of exact exchange and fitting to molecular data, such as experimental heats of formation, allowed even further improvements. This, however, opened a Pandora's Box of fitting possibilities, given the limitless choices of chemical reactions that can be fit. The result is a recent explosion of DFT approximations empirically fit to hundreds, or thousands, of chemical reference data. These fitted density functionals may contain several dozen empirical parameters. What has been lost in this fitting trend is physical modeling based on theory. In this work, we present a density functional comprising our best efforts to model exchange-correlation in DFT using good theory. We compare its performance to that of heavily fit density functionals using the GMTKN55 chemical reference data of Goerigk and co-workers [Phys. Chem. Chem. Phys. 19, 32184 (2017)]. Our density-functional theory, using only a handful of physically motivated pre-factors, competes with the best heavily fit Kohn-Sham functionals in the literature.
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