ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy
复制标题
DOI：
10.1039/c3cp54374a
复制
发表时间：
2014-01-01
影响因子：
3.3
通讯作者：
Head-Gordon, Martin
中科院分区：
文献类型：
--
作者：
Mardirossian, Narbe;Head-Gordon, Martin
提出了一种具有非局域关联的10参数、距离分离、广义梯度近似密度泛函(VV10)。考虑了四阶(m=4)以下的所有16383个线性参数组合，而不是统一地截断交换泛函、同自旋关联泛函和反自旋关联泛函的B97型幂级数不均匀性修正因子。这些泛函分别适合训练集，并在主测试集上验证所得到的参数，以便识别3个最优ICF扩展。通过这一过程发现，在训练集和原始测试集上表现最好的泛函有7个线性参数，另外还有3个来自距离分离和非局部相关的非线性参数。得到的密度泛函omega B97X-V在二次测试集、平行置换的冠烯二聚体以及几个几何数据集上进一步进行了评估。此外，还对omega B97X-V的基组依赖关系和积分网格敏感性进行了分析和记录，以方便泛函的使用。
A 10-parameter, range-separated hybrid (RSH), generalized gradient approximation (GGA) density functional with nonlocal correlation (VV10) is presented. Instead of truncating the B97-type power series inhomogeneity correction factors (ICF) for the exchange, same-spin correlation, and opposite-spin correlation functionals uniformly, all 16383 combinations of the linear parameters up to fourth order (m = 4) are considered. These functionals are individually fit to a training set and the resulting parameters are validated on a primary test set in order to identify the 3 optimal ICF expansions. Through this procedure, it is discovered that the functional that performs best on the training and primary test sets has 7 linear parameters, with 3 additional nonlinear parameters from range-separation and nonlocal correlation. The resulting density functional, omega B97X-V, is further assessed on a secondary test set, the parallel-displaced coronene dimer, as well as several geometry datasets. Furthermore, the basis set dependence and integration grid sensitivity of omega B97X-V are analyzed and documented in order to facilitate the use of the functional.