Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.
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)[rho(1),rho(2)] 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 v(T) are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for v(T). 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.
Fux
Samuel
S
Laboratorium für Physikalische Chemie, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich, Switzerland.
Jacob
Christoph R
CR
Neugebauer
Johannes
J
Visscher
Lucas
L
Reiher
Markus
M
D000641:Ammonia / Q000737:chemistry; D001880:Boranes / Q000737:chemistry; D019281:Dimerization; D004583:Electrons; D004980:Ethane / Q000737:chemistry; D007700:Kinetics; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D011789:Quantum Theory; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D001880:Boranes; D014867:Water; D000641:Ammonia; D004980:Ethane