Abdallah Ammar, Anthony Scemama, Pierre-François Loos, Emmanuel Giner
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引用次数: 0
摘要
虽然选择构型相互作用(SCI)算法可以处理比传统的全 CI 方法大得多的希尔伯特空间,但其计算成本与系统大小的比例关系本质上仍然是指数关系。此外,由于对小电子间距离相关空穴的描述不准确,导致电子能量相对于单电子基集大小的收敛速度很慢。为了缓解这些影响,我们展示了 SCI 的非赫米特、跨相关(TC)版本,它大大压缩了行列式空间,使我们能够用更少的行列式达到给定的精度。此外,我们还注意到,随着基集规模的增大,TC-SCI 能量的收敛速度明显加快。这种压缩程度和能量收敛速度与用于库仑哈密顿相似性变换的相关因子的精确度密切相关。我们在越来越大的基集中对小分子系统进行的系统研究说明了这些影响的严重程度。
Compactification of determinant expansions via transcorrelation.
Although selected configuration interaction (SCI) algorithms can tackle much larger Hilbert spaces than the conventional full CI method, the scaling of their computational cost with respect to the system size remains inherently exponential. In addition, inaccuracies in describing the correlation hole at small interelectronic distances lead to the slow convergence of the electronic energy relative to the size of the one-electron basis set. To alleviate these effects, we show that the non-Hermitian, transcorrelated (TC) version of SCI significantly compactifies the determinant space, allowing us to reach a given accuracy with a much smaller number of determinants. Furthermore, we note a significant acceleration in the convergence of the TC-SCI energy as the basis set size increases. The extent of this compression and the energy convergence rate are closely linked to the accuracy of the correlation factor used for the similarity transformation of the Coulombic Hamiltonian. Our systematic investigation of small molecular systems in increasingly large basis sets illustrates the magnitude of these effects.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
Topical coverage includes:
Theoretical Methods and Algorithms
Advanced Experimental Techniques
Atoms, Molecules, and Clusters
Liquids, Glasses, and Crystals
Surfaces, Interfaces, and Materials
Polymers and Soft Matter
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