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.
引用
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页数:9
相关论文
共 77 条
[1]   Fast noniterative orbital localization for large molecules [J].
Aquilante, Francesco ;
Pedersen, Thomas Bondo ;
Sanchez de Meras, Alfredo ;
Koch, Henrik .
JOURNAL OF CHEMICAL PHYSICS, 2006, 125 (17)
[2]   Cholesky decomposition-based multiconfiguration second-order perturbation theory (CD-CASPT2):: Application to the spin-state energetics of CoIII(diiminato)(NPh) [J].
Aquilante, Francesco ;
Malmqvist, Per-Ake ;
Pedersen, Thomas Bondo ;
Ghosh, Abhik ;
Roos, Bjoern Olof .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2008, 4 (05) :694-702
[3]   Unbiased auxiliary basis sets for accurate two-electron integral approximations [J].
Aquilante, Francesco ;
Lindh, Roland ;
Pedersen, Thomas Bondo .
JOURNAL OF CHEMICAL PHYSICS, 2007, 127 (11)
[4]   Low-cost evaluation of the exchange Fock matrix from Cholesky and density fitting representations of the electron repulsion integrals [J].
Aquilante, Francesco ;
Pedersen, Thomas Bondo ;
Lindh, Roland .
JOURNAL OF CHEMICAL PHYSICS, 2007, 126 (19)
[5]   Quartic scaling evaluation of canonical scaled opposite spin second-order Moller-Plesset correlation energy using Cholesky decompositions [J].
Aquilante, Francesco ;
Pedersen, Thomas Bondo .
CHEMICAL PHYSICS LETTERS, 2007, 449 (4-6) :354-357
[6]   Analytic derivatives for the Cholesky representation of the two-electron integrals [J].
Aquilante, Francesco ;
Lindh, Roland ;
Pedersen, Thomas Bondo .
JOURNAL OF CHEMICAL PHYSICS, 2008, 129 (03)
[7]   Accurate ab initio density fitting for multiconfigurational self-consistent field methods [J].
Aquilante, Francesco ;
Pedersen, Thomas Bondo ;
Lindh, Roland ;
Roos, Bjoern Olof ;
De Meras, Alfredo Sanchez ;
Koch, Henrik .
JOURNAL OF CHEMICAL PHYSICS, 2008, 129 (02)
[8]   Self-consistent molecular Hartree-Fock-Slater calculations - I. The computational procedure [J].
Baerends, E. J. ;
Ellis, D. E. ;
Ros, P. .
CHEMICAL PHYSICS, 1973, 2 (01) :41-51
[9]   Simplifications in the Generation and Transformation of Two-Electron Integrals in Molecular Calculations [J].
Beebe, Nelson H. F. ;
Linderberg, Jan .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1977, 12 (04) :683-705
[10]   Fitting basis sets for the RI-MP2 approximate second-order many-body perturbation theory method [J].
Bernholdt, DE ;
Harrison, RJ .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (05) :1593-1600