Tancogne-Dejean Nicolas, Penz Markus, Ruggenthaler Michael, Rubio Angel
Max Planck Institute for the Structure and Dynamics of Matter and Center for Free-Electron Laser Science, Luruper Chaussee 149, Hamburg 22761, Germany.
European Theoretical Spectroscopy Facility (ETSF), https://www.etsf.eu/.
J Phys Chem A. 2025 Apr 3;129(13):3132-3140. doi: 10.1021/acs.jpca.4c07235. Epub 2025 Mar 19.
The force-balance equation of time-dependent density-functional theory presents a promising route toward obtaining approximate functionals; however, so far, no practical correlation functionals have been derived this way. In this work, starting from a correlated wave function proposed originally by Colle and Salvetti [Theoret. Chim. Acta 37, 329 (1975)], we derive an analytical correlation-energy functional for the ground state based on the force-balance equation. The new functional is compared to the local-density correlation of the homogeneous electron gas, and we find an increased performance for atomic systems, while it performs slightly worse on solids. From this point onward, the new force-based correlation functional can be systematically improved.
含时密度泛函理论的力平衡方程为获得近似泛函提供了一条很有前景的途径；然而，到目前为止，尚未通过这种方式导出实际的关联泛函。在这项工作中，我们从科勒和萨尔韦蒂最初提出的关联波函数出发[《理论化学学报》37, 329 (1975)]，基于力平衡方程推导出了基态的解析关联能泛函。将新泛函与均匀电子气的局域密度关联进行了比较，我们发现它在原子体系上的性能有所提高，而在固体体系上的表现略差。从这一点开始，可以对新的基于力的关联泛函进行系统改进。
