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Analytical gradients of the second‐order Møller–Plesset energy using Cholesky decompositions
Author(s) -
Boström Jonas,
Veryazov Valera,
Aquilante Francesco,
Bondo Pedersen Thomas,
Lindh Roland
Publication year - 2013
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24563
Subject(s) - cholesky decomposition , basis set , møller–plesset perturbation theory , chemistry , basis (linear algebra) , matrix (chemical analysis) , computational chemistry , intermolecular force , quantum mechanics , mathematics , density functional theory , physics , molecule , perturbation theory (quantum mechanics) , geometry , eigenvalues and eigenvectors , chromatography
An algorithm for computing analytical gradients of the second‐order Møller–Plesset (MP2) energy using density fitting (DF) is presented. The algorithm assumes that the underlying canonical Hartree–Fock reference is obtained with the same auxiliary basis set, which we obtain by Cholesky decomposition (CD) of atomic electron repulsion integrals. CD is also used for the negative semidefinite MP2 amplitude matrix. Test calculations on the weakly interacting dimers of the S22 test set (Jurečka et al., Phys. Chem. Chem. Phys . 2006, 8 , 1985) show that the geometry errors due to the auxiliary basis set are negligible. With double‐zeta basis sets, the error due to the DF approximation in intermolecular bond lengths is better than 0.1 pm. The computational time is typically reduced by a factor of 6–7. © 2013 Wiley Periodicals, Inc.