Back
Full-text
Journal article

Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds.

  • 2010-05-06
Published in:
  • The Journal of chemical physics. - 2010
Ammonia
Boranes
Dimerization
Electrons
Ethane
Kinetics
Models, Chemical
Models, Molecular
Molecular Conformation
Quantum Theory
Thermodynamics
Water
English 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.
Language
  • English
Open access status
green
Identifiers
Persistent URL
https://sonar.ch/global/documents/265382
Statistics
Document views: 36 File downloads:
  • Full-text: 0