Analytical Gradients of Hartree-Fock Exchange with Density Fitting Approximations

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Abstract

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.

Detaljer

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

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Teoretisk kemi
Originalspråkengelska
Sidor (från-till)204-212
TidskriftJournal of Chemical Theory and Computation
Volym9
Utgivningsnummer1
StatusPublished - 2013
PublikationskategoriForskning
Peer review utfördJa