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通讯:通过空穴相互作用的零空间消除实现近乎无误差的完全等价相关方法。

Communication: Almost error-free resolution-of-the-identity correlation methods by null space removal of the particle-hole interactions.

机构信息

Chair of Theoretical Chemistry and Center for Integrated Protein Science Munich (CIPSM), Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, D-81377 Munich, Germany.

出版信息

J Chem Phys. 2017 Jun 7;146(21):211106. doi: 10.1063/1.4985085.

Abstract

We present a method to improve upon the resolution-of-the-identity (RI) for correlation methods. While RI is known to allow for drastic speedups, it relies on a cancellation of errors. Our method eliminates the errors introduced by RI which are known to be problematic for absolute energies. In this way, independence of the error compensation assumption for relative energies is also achieved. The proposed method is based on the idea of starting with an oversized RI basis and projecting out all of its unphysical parts. The approach can be easily implemented into existing RI codes and results in an overhead of about 30%, while effectively removing the RI error. In passing, this process alleviates the problem that for many frequently employed basis sets no optimized RI basis sets have been constructed. In this paper, the theory is presented and results are discussed exemplarily for the random phase approximation and Møller-Plesset perturbation theory.

摘要

我们提出了一种改进相关方法中的分辨率-身份(RI)的方法。虽然 RI 已知可以显著提高速度,但它依赖于错误的消除。我们的方法消除了 RI 引入的误差,这些误差已知对绝对能量有问题。通过这种方式,还实现了对相对能量的误差补偿假设的独立性。所提出的方法基于从过大的 RI 基开始并投影出其所有非物理部分的想法。该方法可以轻松地实现到现有的 RI 代码中,并导致大约 30%的开销,同时有效地消除 RI 误差。顺便说一句,这个过程缓解了对于许多经常使用的基集,没有构建优化的 RI 基集的问题。在本文中,理论被提出,并以随机相位近似和 Møller-Plesset 微扰理论为例进行了讨论。

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