, Volume 129, Issue 3-5, pp 453-466
Date: 23 Jan 2011

Calculation of molecular g-tensors using the zeroth-order regular approximation and density functional theory: expectation value versus linear response approaches

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Abstract

Density functional theory (DFT) calculations of molecular g-tensors were implemented as a second derivative property within the two-component relativistic zeroth-order regular approximation (ZORA). g-tensors were computed for systems ranging from light atomic radicals to molecules with heavy d and f block elements. For comparison, computations were also performed with a ZORA first-order derivative approach and with a second derivative method based on the Pauli Hamiltonian. In each set of computations, Slater-type basis sets have been used. The new ZORA implementation allows for non-hybrid and hybrid DFT calculations. A comparison of the PBE non-hybrid and the PBE0 hybrid functional yielded mixed results for our test set. For the lanthanide complex \([\hbox{Ce}(\hbox{DPA})_3]^{3-}\) (DPA = pyridine-2,6-dicarboxylate), calculations of the g-tensor were used to estimate paramagnetic NMR pseudocontact shifts for protons and carbon atoms in the ligands. The results are in reasonable agreement with experimental data.

Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.