TY - JOUR

T1 - On the use of locally dense basis sets in the calculation of EPR hyperfine couplings

T2 - a study on model systems for bio-inorganic Fe and Co complexes

AU - Milhøj, Birgitte Olai

AU - Hedegård, Erik D.

AU - Sauer, Stephan P. A.

PY - 2013/9

Y1 - 2013/9

N2 - The usage of locally dense basis sets in the calculation of Electron Paramagnetic Resonance (EPR) hyperne coupling constants is investigated at the level of Density Functional Theory (DFT) for two model systems of biologically important transition metal complexes: One for the active site in the compound 0 intermediate of cytochrome P450cam, [Fe(OOH)(SH)(en)2]+, and one for the active site in coenzyme B12, [Co(NH3)(CN)(en)2]+. The Fermi contact, spin-dipolar and second order paramagnetic spin-orbit coupling contributions to the hyperne coupling tensors of the metal and the ligating ethylenediamine N atoms are calculated, and their dependence on the basis set for the remaining atoms are investigated. Core property basis sets are employed for the metals (aug-cc-pVTZ-Juc) and their equatorially coordinating N atoms (aug-cc-pVTZ-J or 6-31G-Juc analogues to the Pople style basis sets used for the remaining atoms), while smaller correlation-consistent or Pople style basis sets are used for the remaining, so-called non-coupled, atoms. Most of the investigated basis set combinations are found to give results which dier by less than 1% from the results obtained with core property basis sets on all atoms. We nd thus for the cytochrome model system that using the small 6-31G(d) basis set on the non-coupled atoms together with core property basis sets on the Fe and N atoms gives essentially converged results. It is found to be mostly the second order paramagnetic spin-orbit interaction that demands the use of larger basis sets on the non-coupled atoms. If, however, an error of less than 0.5 MHz is sucient any basis set can be used for the non-coupled atoms. For the cobalt containing model system the 6-31G(2d) basis set generally gives results within 1% of the reference value.

AB - The usage of locally dense basis sets in the calculation of Electron Paramagnetic Resonance (EPR) hyperne coupling constants is investigated at the level of Density Functional Theory (DFT) for two model systems of biologically important transition metal complexes: One for the active site in the compound 0 intermediate of cytochrome P450cam, [Fe(OOH)(SH)(en)2]+, and one for the active site in coenzyme B12, [Co(NH3)(CN)(en)2]+. The Fermi contact, spin-dipolar and second order paramagnetic spin-orbit coupling contributions to the hyperne coupling tensors of the metal and the ligating ethylenediamine N atoms are calculated, and their dependence on the basis set for the remaining atoms are investigated. Core property basis sets are employed for the metals (aug-cc-pVTZ-Juc) and their equatorially coordinating N atoms (aug-cc-pVTZ-J or 6-31G-Juc analogues to the Pople style basis sets used for the remaining atoms), while smaller correlation-consistent or Pople style basis sets are used for the remaining, so-called non-coupled, atoms. Most of the investigated basis set combinations are found to give results which dier by less than 1% from the results obtained with core property basis sets on all atoms. We nd thus for the cytochrome model system that using the small 6-31G(d) basis set on the non-coupled atoms together with core property basis sets on the Fe and N atoms gives essentially converged results. It is found to be mostly the second order paramagnetic spin-orbit interaction that demands the use of larger basis sets on the non-coupled atoms. If, however, an error of less than 0.5 MHz is sucient any basis set can be used for the non-coupled atoms. For the cobalt containing model system the 6-31G(2d) basis set generally gives results within 1% of the reference value.

KW - Faculty of Science

KW - EPR spectroscopy

KW - Metalloproteins

KW - Computational Chemistry

KW - Quantum Chemistry

U2 - 10.2174/1877944103666140110225818

DO - 10.2174/1877944103666140110225818

M3 - Journal article

VL - 3

SP - 270

EP - 283

JO - Current Inorganic Chemistry

JF - Current Inorganic Chemistry

SN - 1877-9441

IS - 3

ER -