Localized hybrid exchange-correlation
potentials: construction and performance in DFT calculations of NMR and EPR parameters
Dr. A.ARBUZNIKOV
Université de Würzburg, Allemagne
Jeudi 17 juin 2004, 11h00
Traditional non-local and non-multiplicative exchange-correlation
potentials containing an admixture of Hartree-Fock exchange have been
converted into local and multiplicative Kohn-Sham potentials. The
optimized effective potential method (OEP) ("Localized Hartree-Fock"
(LHF) approximation [1]) has been used for this purpose. The resulting
localized hybrid potentials have been evaluated in DFT calculations of
magnetic-resonance parameters, namely, nuclear shielding constants of
main-group molecules [2], and electronic g-tensors of 3d transition-metal
complexes [3].
In contrast to non-local hybrid potentials, optimum performance of
the present, localized potentials is found at very similar amounts of
exact-exchange admixture for both nuclear shieldings of main-group
molecules and g-tensors of transition-metal compounds. A simple
non-empirical way of getting nearly-optimal exact exchange admixture for
each system of interest has been found as well.
Our approach yields encouraging results and presents a basis for
further improvement of property-oriented exchange-correlation potentials.
References:
[1] F. Della Sala, A. Goerling, J. Chem. Phys. 115 (2001) 5718.
[2] A. V. Arbuznikov, M. Kaupp, Chem. Phys. Lett. 386 (2004) 8.
[2] A. V. Arbuznikov, M. Kaupp, Chem. Phys. Lett. 391 (2004) 16.