An efficient implementation of two-component relativistic exact-decoupling methods for large molecules
An efficient implementation of two-component relativistic exact-decoupling methods for large molecules
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DOI：
10.1063/1.4803693
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发表时间：
2013-05-14
影响因子：
4.4
通讯作者：
Reiher, Markus
中科院分区：
文献类型：
--
作者：
Peng, Daoling;Middendorf, Nils;Reiher, Markus
我们提出了一个有效的算法，一个和两个组件的相对论精确去耦计算。自旋轨道耦合，从而考虑到相对论变换（单电子）哈密顿量的评价。由于相对论性退耦变换必须用原函数计算，相对论性单电子哈密顿量的构造成为整个大分子计算的瓶颈。对于已建立的精确解耦协议，建立了一个最小矩阵运算次数，并进行了详细的讨论。此外，我们应用我们最近发展的局部DLU方案[D. Peng和M. Reiher，J.Chem.Phys.136，244108（2012）]以加速该步骤。与我们的新的实现两个组件的相对论密度泛函计算可以调用分辨率的身份密度拟合近似和（阿贝尔以及非阿贝尔）点群对称性，以加速精确的去耦和两个电子的一部分。我们的实现的能力示出的例子中的银团簇与多达309个原子，其中的内聚能计算和外推到散装。(C)2013 AIP Publishing LLC.
We present an efficient algorithm for one- and two-component relativistic exact-decoupling calculations. Spin-orbit coupling is thus taken into account for the evaluation of relativistically transformed (one-electron) Hamiltonian. As the relativistic decoupling transformation has to be evaluated with primitive functions, the construction of the relativistic one-electron Hamiltonian becomes the bottleneck of the whole calculation for large molecules. For the established exact-decoupling protocols, a minimal matrix operation count is established and discussed in detail. Furthermore, we apply our recently developed local DLU scheme [D. Peng and M. Reiher, J. Chem. Phys. 136, 244108 (2012)] to accelerate this step. With our new implementation two-component relativistic density functional calculations can be performed invoking the resolution-of-identity density-fitting approximation and (Abelian as well as non-Abelian) point group symmetry to accelerate both the exact-decoupling and the two-electron part. The capability of our implementation is illustrated at the example of silver clusters with up to 309 atoms, for which the cohesive energy is calculated and extrapolated to the bulk. (C) 2013 AIP Publishing LLC.