TY - JOUR

T1 - Optimizing the structure of Tetracyanoplatinate(II)

T2 - a comparison of relativistic density functional theory methods

AU - Dohn, Asmus Ougaard

AU - Møller, Klaus Braagaard

AU - Sauer, Stephan P. A.

PY - 2013

Y1 - 2013

N2 - The geometry of tetracyanoplatinate(II) (TCP) has been optimized with density functional theory (DFT) calculations in order to compare different computational strategies. Two approximate scalar relativistic methods, i.e. the scalar zeroth-order regular approximation (ZORA) and non-relativistic calculations with relativistic effective core potentials (ECPs), were benchmarked against the four-component fully relativistic approach using the Dirac-Coulomb Hamiltonian and all-electron non-relativistic calculations. We find that the 5% contraction of the platinum-carbon bond due to relativistic effects is almost quantitatively reproduced in the ZORA and ECP calculations. In addition, the effect of the exchange-correlation functional and one-electron basis set was studied by employing the two generalized gradient approximation (GGA) functionals, BLYP and PBE, as well as their hybrid version B3LYP and PBE0 in combination with both correlation consistent and Ahlrichs type basis sets. The platinumcarbon bond length (relativistic or non-relativistic) is approximately 1% shorter on using the PBE exchange-correlation functional compared to the BLYP functional but including exact exchange has no significant effect. For the C-N bond these trends are reversed and an order of magnitude smaller. With respect to the basis set dependence we observed that a triple zeta basis set with polarization functions gives in general sufficiently converged results, but while for the Pt-C bond it is advantageous to include extra diffuse functions, this did not turn out to be important for the C-N bond.

AB - The geometry of tetracyanoplatinate(II) (TCP) has been optimized with density functional theory (DFT) calculations in order to compare different computational strategies. Two approximate scalar relativistic methods, i.e. the scalar zeroth-order regular approximation (ZORA) and non-relativistic calculations with relativistic effective core potentials (ECPs), were benchmarked against the four-component fully relativistic approach using the Dirac-Coulomb Hamiltonian and all-electron non-relativistic calculations. We find that the 5% contraction of the platinum-carbon bond due to relativistic effects is almost quantitatively reproduced in the ZORA and ECP calculations. In addition, the effect of the exchange-correlation functional and one-electron basis set was studied by employing the two generalized gradient approximation (GGA) functionals, BLYP and PBE, as well as their hybrid version B3LYP and PBE0 in combination with both correlation consistent and Ahlrichs type basis sets. The platinumcarbon bond length (relativistic or non-relativistic) is approximately 1% shorter on using the PBE exchange-correlation functional compared to the BLYP functional but including exact exchange has no significant effect. For the C-N bond these trends are reversed and an order of magnitude smaller. With respect to the basis set dependence we observed that a triple zeta basis set with polarization functions gives in general sufficiently converged results, but while for the Pt-C bond it is advantageous to include extra diffuse functions, this did not turn out to be important for the C-N bond.

KW - Faculty of Science

KW - Relativistic Effects

KW - 4-Component Calculations

KW - Transition metal complex

KW - Geometry Optimization

KW - Density functional theory

KW - Platinum

U2 - 10.2174/1877944103666140110230100

DO - 10.2174/1877944103666140110230100

M3 - Journal article

VL - 3

SP - 213

EP - 219

JO - Current Inorganic Chemistry

JF - Current Inorganic Chemistry

SN - 1877-9441

IS - 3

ER -