Analytical Gradients of Hartree-Fock Exchange with Density Fitting Approximations

Forskningsoutput: TidskriftsbidragArtikel i vetenskaplig tidskrift


We extend the local exchange (LK) algorithm [Aquilante, F.; Pedersen, T. B.; Lindh, R. J. Chem. Phys. 2007, 126, 194106] to the calculation of analytical gradients with density fitting. We discuss the features of the screening procedure and demonstrate the possible advantages of using this formulation, which is easily interfaced to a standard integral-direct gradient code. With auxiliary basis sets obtained from Cholesky decomposition of atomic or molecular integral blocks with a decomposition threshold of 10(-4)E(h), typical errors due to the density fitting in bond lengths, bond angles, and dihedral angles are 0.1 pm, 0.1 degrees, and 0.5 degrees, respectively. The overall speedup of geometry optimizations is about 1 order of magnitude for atomic natural-orbital-type basis sets but much less pronounced for correlation-consistent basis sets.


  • Jonas Boström
  • Francesco Aquilante
  • Thomas Bondo Pedersen
  • Roland Lindh
Enheter & grupper

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Teoretisk kemi
Sidor (från-till)204-212
TidskriftJournal of Chemical Theory and Computation
StatusPublished - 2013
Peer review utfördJa