1. Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.
- Author
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Fux, Samuel, Jacob, Christoph R., Neugebauer, Johannes, Visscher, Lucas, and Reiher, Markus
- Subjects
DENSITY functionals ,HYDROGEN bonding ,STOPPING power (Nuclear physics) ,QUANTUM chemistry ,QUANTUM theory ,ELECTRON distribution - Abstract
The frozen-density embedding (FDE) scheme [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] relies on the use of approximations for the kinetic-energy component v
T [ρ1 ,ρ2 ] of the embedding potential. While with approximations derived from generalized-gradient approximation kinetic-energy density functional weak interactions between subsystems such as hydrogen bonds can be described rather accurately, these approximations break down for bonds with a covalent character. Thus, to be able to directly apply the FDE scheme to subsystems connected by covalent bonds, improved approximations to vT are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for vT . We present accurate embedding potentials for a selected set of model systems, in which the subsystems are connected by hydrogen bonds of various strength (water dimer and F–H–F- ), a coordination bond (ammonia borane), and a prototypical covalent bond (ethane). These accurate potentials are analyzed and compared to those obtained from popular kinetic-energy density functionals. [ABSTRACT FROM AUTHOR]- Published
- 2010
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