Efficient Implementation of Relativistic Exact-decoupling Methods for Large Molecules

来源 :第七届国际理论化学、分子模拟和生命科学研讨会暨科学计算和模拟软件发展平台学术交流会 | 被引量 : 0次 | 上传用户:poodlihua
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  We present an efficient algorithm for relativistic exact-decoupling[1] calculations.Spin-orbit coupling is taken into account for the evaluation of relativistically transformed 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[2] to accelerate this step.Its computational scaling can be reduced to linear scaling by employing the neighboring-atomic-blocks approximation.If a large molecule contains many light atoms,the computational costs can be further reduced by employing a well-defined non-relativistic approximation for these light atoms without significant loss of accuracy.With our new implementation two-component relativistic density functional calculations can be performed invoking the resolution-of-identity density-fitting approximation and 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.
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