Partitioning the DFT exchange-correlation energy in line with the interacting quantum atoms approach
Por:
Francisco, E., Casals-Sainz, J. L., Rocha-Rinza, Tomas, Martin Pendas, A.
Publicada:
29 jun 2016
Categoría:
Physical and Theoretical Chemistry
Resumen:
The interacting quantum atoms (IQA) energy partition has given important
insights about different systems and processes in theoretical chemistry.
Given its intrinsic dependence on first- and second-order density
matrices, IQA is only cleanly defined within wavefunction methods. This
means that, despite the importance of density functional theory (DFT) in
electronic structure methods, a neat IQA-DFT implementation is not
straightforward. This work addresses this issue through a new
implementation of IQA within the Kohn-Sham formalism of DFT in
conjunction with hybrid and non-hybrid functionals that contributes
further to that already presented (Maxwell et al. in Phys Chem Chem
Phys, 2016). For this purpose, we use additive exchange-correlation (xc)
energies, defined within the IQA approach, to scale the one- and
two-atom terms of the Kohn-Sham xc energy. This leads to an exact
partition of the xc DFT energy of a molecule into intra-atomic and
inter-atomic contributions. The suggested method is illustrated with
several molecules together with some of the most popular local and
hybrid DFT functionals. Overall, we anticipate that the approach put
forward in this work will prove useful in getting further insights of
phenomena in chemistry which are properly described with DFT .
Filiaciones:
Francisco, E.:
Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
Casals-Sainz, J. L.:
Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
Rocha-Rinza, Tomas:
Univ Nacl Autonoma Mexico, Inst Quim, Ciudad Univ, Mexico City 04510, DF, Mexico
Martin Pendas, A.:
Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
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