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Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations. \ud

By O.B. Lutnæs, A.M. Teale, T. Helgaker, D.J. Tozer, K. Ruud and J. Gauss


An accurate set of benchmark rotational g tensors and magnetizabilities are calculated using coupled-cluster singles-doubles (CCSD) theory and coupled-cluster single-doubles-perturbative-triples [CCSD(T)] theory, in a variety of basis sets consisting of (rotational) London atomic orbitals. The accuracy of the results obtained is established for the rotational g tensors by careful comparison with experimental data, taking into account zero-point vibrational corrections. After an analysis of the basis sets employed, extrapolation techniques are used to provide estimates of the basis-set-limit quantities, thereby establishing an accurate benchmark data set. The utility of the data set is demonstrated by examining a wide variety of density functionals for the calculation of these properties. None of the density-functional methods are competitive with the CCSD or CCSD(T) methods. The need for a careful consideration of vibrational effects is clearly illustrated. Finally, the pure coupled-cluster results are compared with the results of density-functional calculations constrained to give the same electronic density. The importance of current dependence in exchange–correlation functionals is discussed in light of this comparison

Topics: Coupled cluster calculations, Density functional theory, Perturbation theory, Rotational states, Vibrational states
Publisher: American Institute of Physics
Year: 2009
DOI identifier: 10.1063/1.3242081
OAI identifier: oai:dro.dur.ac.uk.OAI2:10118

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