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Atomic Cholesky decompositions: A route to unbiased auxiliary basis sets for density fitting approximation with tunable accuracy and efficiency
被引:194
作者:
Aquilante, Francesco
[1
]
Gagliardi, Laura
[1
]
Pedersen, Thomas Bondo
[2
]
Lindh, Roland
[2
]
机构:
[1] Univ Geneve Sci 2, Dept Phys Chem, CH-1211 Geneva 4, Switzerland
[2] Lund Univ, Ctr Chem, Dept Theoret Chem, S-22100 Lund, Sweden
基金:
瑞士国家科学基金会;
瑞典研究理事会;
关键词:
ab initio calculations;
density functional theory;
Gaussian processes;
orbital calculations;
ELECTRONIC-STRUCTURE CALCULATIONS;
FUNCTIONAL THEORY CALCULATIONS;
COUPLED-CLUSTER THEORY;
LINEAR-RESPONSE THEORY;
IDENTITY APPROXIMATION;
ENERGY CALCULATIONS;
COULOMB POTENTIALS;
OPTICAL-ROTATION;
INTEGRALS;
MATRIX;
D O I:
10.1063/1.3116784
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
Cholesky decomposition of the atomic two-electron integral matrix has recently been proposed as a procedure for automated generation of auxiliary basis sets for the density fitting approximation [F. Aquilante , J. Chem. Phys. 127, 114107 (2007)]. In order to increase computational performance while maintaining accuracy, we propose here to reduce the number of primitive Gaussian functions of the contracted auxiliary basis functions by means of a second Cholesky decomposition. Test calculations show that this procedure is most beneficial in conjunction with highly contracted atomic orbital basis sets such as atomic natural orbitals, and that the error resulting from the second decomposition is negligible. We also demonstrate theoretically as well as computationally that the locality of the fitting coefficients can be controlled by means of the decomposition threshold even with the long-ranged Coulomb metric. Cholesky decomposition-based auxiliary basis sets are thus ideally suited for local density fitting approximations.
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