Accelerating Kohn-Sham response theory using density fitting and the auxiliary-density-matrix method
Accelerating Kohn-Sham response theory using density fitting and the auxiliary-density-matrix method
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DOI：
10.1002/qua.25639
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发表时间：
2018-08-15
影响因子：
2.2
通讯作者：
Kjaergaard, Thomas
中科院分区：
文献类型：
--
作者：
Kumar, Chandan;Fliegl, Heike;Kjaergaard, Thomas
Larsen等人的基于原子轨道的响应理论的公式化的扩展，JCP 113，8909（2000）。这个新的框架已在LSDalton中实现，并允许使用Kohn-Sham密度泛函理论，通过流行的分辨率的身份近似以及密度矩阵方法（ADMM）的库仑和交换贡献的响应方程的近似处理。我们提出了基准计算的基态能量以及线性和二次响应特性：垂直激发能，极化率和超极化率。这些近似的质量在一个范围内的基组进行评估对参考计算在一个大aug-pcseg-4的基础。我们的研究结果证实，密度拟合的库仑贡献，可以毫不犹豫地用于所有的研究性质。交换的ADMM处理示出产生高精度的基态和激发能，而极化率和超极化率的性能增益是在精度的成本。激发能的四聚体模型的光系统I的P700特殊色素的单位组成的已被研究，以证明一个大的系统的代码的适用性。
An extension of the formulation of the atomic-orbital-based response theory of Larsen et al., JCP 113, 8909 (2000) is presented. This new framework has been implemented in LSDalton and allows for the use of Kohn-Sham density-functional theory with approximate treatment of the Coulomb and Exchange contributions to the response equations via the popular resolution-of-the-identity approximation as well as the auxiliary-density matrix method (ADMM). We present benchmark calculations of ground-state energies as well as the linear and quadratic response properties: vertical excitation energies, polarizabilities, and hyperpolarizabilities. The quality of these approximations in a range of basis sets is assessed against reference calculations in a large aug-pcseg-4 basis. Our results confirm that density fitting of the Coulomb contribution can be used without hesitation for all the studied properties. The ADMM treatment of exchange is shown to yield high accuracy for ground-state and excitation energies, whereas for polarizabilities and hyperpolarizabilities the performance gain comes at a cost of accuracy. Excitation energies of a tetrameric model consisting of units of the P700 special pigment of photosystem I have been studied to demonstrate the applicability of the code for a large system.