论文标题
下一代非本地范德华密度功能
Next-generation non-local van der Waals density functional
论文作者
论文摘要
1990年代已经构思了非本地密度功能理论的基本思想 - 能够可靠地捕获范德华相互作用。 2004年,一篇开创性的论文介绍了第一个称为VDW-DF的实用非本地交易相关功能,该功能已广泛成功,并为进一步的研究奠定了基础。但是,从那时起,VDW-DF的功能形式一直保持不变。几种成功的修改将原始功能与不同的(本地)交换功能配对以提高性能,而后继VDW-DF2也更新了一个内部参数。从近二十年的开发和测试中汇集了不同的见解,我们提出了下一代非本地相关功能,称为VDW-DF3,在该功能中,我们改变了功能形式,同时又忠于原始设计理念。尽管许多流行的功能在范德华复合物的结合分离周围表现出良好的性能,但它们通常会在较大的分离下造成严重的误差。借助VDW-DF3,我们通过利用近期发现且在很大程度上不受限制的VDW-DF框架内的自由度来解决这个问题,该框架可以通过经验输入来限制,从而使我们的功能性半经验。对于两种不同的参数化,我们根据大量研究的测试用例进行基准测试VDW-DF3,并将我们的结果与最受欢迎的功能进行比较,在各种系统中找到了良好的性能,并在较大的分离下的准确性显着提高。最后,我们讨论了当前VDW-DF框架中可实现的性能,VDW-DF3提供的功能设计的灵活性,以及非本地范德WAALS密度功能理论的未来方向。
The fundamental ideas for a non-local density functional theory -- capable of reliably capturing van der Waals interaction -- were already conceived in the 1990's. In 2004, a seminal paper introduced the first practical non-local exchange-correlation functional called vdW-DF, which has become widely successful and laid the foundation for much further research. However, since then, the functional form of vdW-DF has remained unchanged. Several successful modifications paired the original functional with different (local) exchange functionals to improve performance and the successor vdW-DF2 also updated one internal parameter. Bringing together different insights from almost two decades of development and testing, we present the next-generation non-local correlation functional called vdW-DF3, in which we change the functional form while staying true to the original design philosophy. Although many popular functionals show good performance around the binding separation of van der Waals complexes, they often result in significant errors at larger separations. With vdW-DF3, we address this problem by taking advantage of a recently uncovered and largely unconstrained degree of freedom within the vdW-DF framework that can be constrained through empirical input, making our functional semi-empirical. For two different parameterizations, we benchmark vdW-DF3 against a large set of well-studied test cases and compare our results with the most popular functionals, finding good performance in general for a wide array of systems and a significant improvement in accuracy at larger separations. Finally, we discuss the achievable performance within the current vdW-DF framework, the flexibility in functional design offered by vdW-DF3, as well as possible future directions for non-local van der Waals density functional theory.