Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Chem Phys. 2013 Jul 14;139(2):024110. doi: 10.1063/1.4812689.
This paper advocates development of a new class of double-hybrid (DH) density functionals where the energy is fully orbital optimized (OO) in presence of all correlation, rather than using a final non-iterative second order perturbative correction. The resulting OO-DH functionals resolve a number of artifacts associated with conventional DH functionals, such as first derivative discontinuities. To illustrate the possibilities, two non-empirical OO-DH functionals are obtained from existing DH functionals based on PBE: OO-PBE0-DH and OO-PBE0-2. Both functionals share the same functional form, with parameters determined on the basis of different physical considerations. The new functionals are tested on a variety of bonded, non-bonded and symmetry-breaking problems.
本文提倡开发一类新的双杂化 (DH) 密度泛函，其中在存在所有相关项的情况下对能量进行完全轨道优化 (OO)，而不是使用最终的非迭代二阶微扰修正。所得到的 OO-DH 泛函解决了与传统 DH 泛函相关的许多伪像，例如一阶导数不连续。为了说明这些可能性，从基于 PBE 的现有 DH 泛函中获得了两个非经验的 OO-DH 泛函：OO-PBE0-DH 和 OO-PBE0-2。这两个泛函具有相同的函数形式，参数是根据不同的物理考虑确定的。新的泛函在各种键合、非键合和对称破缺问题上进行了测试。
