Analytical gradients of the second-order Møller–Plesset energy using Cholesky decompositions
Article first published online: 25 OCT 2013
Copyright © 2013 Wiley Periodicals, Inc.
International Journal of Quantum Chemistry
Volume 114, Issue 5, pages 321–327, 5 March 2014
How to Cite
How to cite this article: Int. J. Quantum Chem. 2014, 114, 321–327. DOI: 10.1002/qua.24563, , , , .
- Issue published online: 20 JAN 2014
- Article first published online: 25 OCT 2013
- Manuscript Accepted: 23 SEP 2013
- Manuscript Received: 22 SEP 2013
- Manuscript Revised: 22 SEP 2013
- Research Council of Norway (Centre of Excellence Grant). Grant Number: 179568/V30
- Swedish Research Council. Grant Number: 2012-3910
- Cholesky decomposition;
- density fitting;
- analytic gradients
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.