Nuclear cusp condition for the orbital-free effective embedding potential

Journal of Chemical Physics 129, 74107 (2008)

Nuclear cusp condition for the orbital-free effective embedding potential

J.M García-Lastra, J.W. Kaminski, T.A. Wesolowski

A strategy to construct approximants to the kinetic-energy-functional dependent component of the effective potential in one-electron equations for orbitals embedded in a frozen-density environment _Eqs. 20 and _21 in Wesolowski and Warshel, J. Phys. Chem. 97, (1993) 8050 is proposed. In order to improve the local behavior of the orbital-free effective embedding potential near nuclei in the environment, the exact behavior is taken into account. As a result, the properties depending on the quality of this potential are invariably improved compared to the ones obtained using conventional approximants which violated the considered exact condition. The approximants obtained following the proposed strategy and especially the simplest one constructed in this work are nondecomposable, i.e., cannot be used to obtain the analytic expression for the functional of the total kinetic energy.

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Doi
http://dx.doi.org/10.1063/1.2969814

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