Derivation of general analytic gradient expressions for densityfitted postHartreeFock methods: An efficient implementation for the densityfitted secondorder Møller–Plesset perturbation theory
Abstract
General analytic gradient expressions (with the frozencore approximation) are presented for densityfitted postHF methods. An efficient implementation of frozencore analytic gradients for the secondorder Møller–Plesset perturbation theory (MP2) with the densityfitting (DF) approximation (applying to both reference and correlation energies), which is denoted as DFMP2, is reported. The DFMP2 method is applied to a set of alkanes, conjugated dienes, and noncovalent interaction complexes to compare the computational cost of single point analytic gradients with MP2 with the resolution of the identity approach (RIMP2) [F. Weigend and M. Häser, Theor. Chem. Acc. 97, 331 (1997); R. A. Distasio, R. P. Steele, Y. M. Rhee, Y. Shao, and M. HeadGordon, J. Comput. Chem. 28, 839 (2007)]. In the RIMP2 method, the DF approach is used only for the correlation energy. Our results demonstrate that the DFMP2 method substantially accelerate the RIMP2 method for analytic gradient computations due to the reduced input/output (I/O) time. Because in the DFMP2 method the DF approach is used for both reference and correlation energies, the storage of 4index electron repulsion integrals (ERIs) are avoided, 3index ERI tensors are employed instead. Further, as in case of integrals, our gradient equation is completely avoid construction or storage of themore »
 Authors:

 Department of Chemistry, Atatürk University, Erzurum 25240, Turkey and Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)
 Publication Date:
 OSTI Identifier:
 22308892
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 141; Journal Issue: 12; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKANES; BOND LENGTHS; COMPARATIVE EVALUATIONS; DENSITY MATRIX; ELECTRONS; HARTREEFOCK METHOD; INTERACTIONS; PARTICLES; SOLUTIONS
Citation Formats
Bozkaya, Uğur. Derivation of general analytic gradient expressions for densityfitted postHartreeFock methods: An efficient implementation for the densityfitted secondorder Møller–Plesset perturbation theory. United States: N. p., 2014.
Web. doi:10.1063/1.4896235.
Bozkaya, Uğur. Derivation of general analytic gradient expressions for densityfitted postHartreeFock methods: An efficient implementation for the densityfitted secondorder Møller–Plesset perturbation theory. United States. https://doi.org/10.1063/1.4896235
Bozkaya, Uğur. 2014.
"Derivation of general analytic gradient expressions for densityfitted postHartreeFock methods: An efficient implementation for the densityfitted secondorder Møller–Plesset perturbation theory". United States. https://doi.org/10.1063/1.4896235.
@article{osti_22308892,
title = {Derivation of general analytic gradient expressions for densityfitted postHartreeFock methods: An efficient implementation for the densityfitted secondorder Møller–Plesset perturbation theory},
author = {Bozkaya, Uğur},
abstractNote = {General analytic gradient expressions (with the frozencore approximation) are presented for densityfitted postHF methods. An efficient implementation of frozencore analytic gradients for the secondorder Møller–Plesset perturbation theory (MP2) with the densityfitting (DF) approximation (applying to both reference and correlation energies), which is denoted as DFMP2, is reported. The DFMP2 method is applied to a set of alkanes, conjugated dienes, and noncovalent interaction complexes to compare the computational cost of single point analytic gradients with MP2 with the resolution of the identity approach (RIMP2) [F. Weigend and M. Häser, Theor. Chem. Acc. 97, 331 (1997); R. A. Distasio, R. P. Steele, Y. M. Rhee, Y. Shao, and M. HeadGordon, J. Comput. Chem. 28, 839 (2007)]. In the RIMP2 method, the DF approach is used only for the correlation energy. Our results demonstrate that the DFMP2 method substantially accelerate the RIMP2 method for analytic gradient computations due to the reduced input/output (I/O) time. Because in the DFMP2 method the DF approach is used for both reference and correlation energies, the storage of 4index electron repulsion integrals (ERIs) are avoided, 3index ERI tensors are employed instead. Further, as in case of integrals, our gradient equation is completely avoid construction or storage of the 4index twoparticle density matrix (TPDM), instead we use 2 and 3index TPDMs. Hence, the I/O bottleneck of a gradient computation is significantly overcome. Therefore, the cost of the generalizedFock matrix (GFM), TPDM, solution of Zvector equations, the back transformation of TPDM, and integral derivatives are substantially reduced when the DF approach is used for the entire energy expression. Further application results show that the DF approach introduce negligible errors for closedshell reaction energies and equilibrium bond lengths.},
doi = {10.1063/1.4896235},
url = {https://www.osti.gov/biblio/22308892},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 12,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}