Modrzejewski Marcin, Hapka Michal, Chalasinski Grzegorz, Szczesniak Malgorzata M
Faculty of Chemistry, University of Warsaw , 02-093 Warsaw, Pasteura 1, Poland.
Department of Chemistry, Oakland University , Rochester, Michigan 48309-4477, United States.
J Chem Theory Comput. 2016 Aug 9;12(8):3662-73. doi: 10.1021/acs.jctc.6b00406. Epub 2016 Jul 29.
We devise a scheme for converting an existing exchange functional into its range-separated hybrid variant. The underlying exchange hole of the Becke-Roussel type has the exact second-order expansion in the interelectron distance. The short-range part of the resulting range-separated exchange energy depends on the kinetic energy density and the Laplacian even if the base functional lacks the dependence on these variables. The most successful practical realization of the scheme, named LC-PBETPSS, combines the range-separated Perdew-Burke-Ernzerhof (PBE) exchange lifted to the hybrid meta-generalized gradient approximation rung and the Tao-Perdew-Staroverov-Scuseria (TPSS) correlation. The value of the range-separation parameter is estimated theoretically and confirmed by empirical optimization. The D3 dispersion correction is recommended for all energy computations employing the presented functional. Numerical tests show remarkably robust performance of the method for noncovalent interaction energies, barrier heights, main-group thermochemistry, and excitation energies.
我们设计了一种方案，用于将现有的交换泛函转换为其范围分离的杂化变体。Becke-Roussel型的潜在交换空穴在电子间距离上具有精确的二阶展开。即使基础泛函不依赖于这些变量，所得范围分离交换能的短程部分仍取决于动能密度和拉普拉斯算子。该方案最成功的实际实现称为LC-PBETPSS，它将提升到杂化元广义梯度近似等级的范围分离的Perdew-Burke-Ernzerhof（PBE）交换与Tao-Perdew-Staroverov-Scuseria（TPSS）相关相结合。范围分离参数的值通过理论估计并经经验优化得到确认。对于使用所提出泛函的所有能量计算，建议采用D3色散校正。数值测试表明，该方法在非共价相互作用能、势垒高度、主族热化学和激发能方面具有非常稳健的性能。
