Fragment approach to constrained density functional theory calculations using Daubechies wavelets
Abstract
In a recent paper, we presented a linear scaling KohnSham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused asis, i.e., without reoptimization, for chargeconstrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are rototranslated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.
 Authors:

 Université de Grenoble Alpes, CEA, INACSP2M, LSim, F38000 Grenoble (France)
 Publication Date:
 OSTI Identifier:
 22415983
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 142; Journal Issue: 23; Other Information: (c) 2015 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; ACCURACY; CHEMICAL PROPERTIES; DENSITY FUNCTIONAL METHOD; DENSITY MATRIX; FLEXIBILITY; GROUND STATES
Citation Formats
Ratcliff, Laura E., Email: lratcliff@anl.gov, Université de Grenoble Alpes, CEA, INACSP2M, LSim, F38000 Grenoble, Genovese, Luigi, Mohr, Stephan, and Deutsch, Thierry. Fragment approach to constrained density functional theory calculations using Daubechies wavelets. United States: N. p., 2015.
Web. doi:10.1063/1.4922378.
Ratcliff, Laura E., Email: lratcliff@anl.gov, Université de Grenoble Alpes, CEA, INACSP2M, LSim, F38000 Grenoble, Genovese, Luigi, Mohr, Stephan, & Deutsch, Thierry. Fragment approach to constrained density functional theory calculations using Daubechies wavelets. United States. doi:10.1063/1.4922378.
Ratcliff, Laura E., Email: lratcliff@anl.gov, Université de Grenoble Alpes, CEA, INACSP2M, LSim, F38000 Grenoble, Genovese, Luigi, Mohr, Stephan, and Deutsch, Thierry. Sun .
"Fragment approach to constrained density functional theory calculations using Daubechies wavelets". United States. doi:10.1063/1.4922378.
@article{osti_22415983,
title = {Fragment approach to constrained density functional theory calculations using Daubechies wavelets},
author = {Ratcliff, Laura E., Email: lratcliff@anl.gov and Université de Grenoble Alpes, CEA, INACSP2M, LSim, F38000 Grenoble and Genovese, Luigi and Mohr, Stephan and Deutsch, Thierry},
abstractNote = {In a recent paper, we presented a linear scaling KohnSham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused asis, i.e., without reoptimization, for chargeconstrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are rototranslated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.},
doi = {10.1063/1.4922378},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 23,
volume = 142,
place = {United States},
year = {2015},
month = {6}
}