The Rotational <i>g</i> Tensor as a Benchmark for Density-Functional Theory Calculations of Molecular Magnetic Properties

Wilson, David J.; Mohn, Chris E.; Helgaker, Trygve

doi:10.1021/ct050101t

Cited by 30 publications

(31 citation statements)

References 78 publications

(141 reference statements)

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“…This relationship means that the implementation of rotational g tensors can be achieved as a straightforward extension to any implementation of LAO magnetizabilities. We use the implementation of LAOs in the DALTON quantum-chemistry package for the Hartree-Fock and Kohn-Sham calculations, [4][5][6] and the recent implementation in the Mainz-Austin-Budapest version of the ACES II package for the coupled-cluster calculations. 6,7 …”

Section: A Ensuring Gauge-origin Independencementioning

confidence: 99%

“…A variety of methods has been used to calculate these quantities previously, including Hartree-Fock theory, 6,30-32 multiconfigurational self-consistent-field ͑MCSCF͒ theory, [33][34][35][36][37][38][39][40] Møller-Plesset theory, 39 [51][52][53] and DFT. 5,11,54 In the present work, we calculate the ZPVCs to the rotational g tensor and the magnetizability using perturbation theory, following Ref. 40 using DFT.…”

Section: B Comparison With Experimental Valuesmentioning

confidence: 99%

“…The latter has been shown to give high-accuracy results in a variety of applications and is typically the benchmark against which other methodologies are compared. Recently, it has become possible to utilize DFT and coupled-cluster methods in conjunction with ͑rotational͒ London atomic orbitals ͑LAOs͒ [4][5][6][7] to calculate a variety of magnetic properties. In the present paper, we focus on a set of 28 small molecules in order to provide a set of accurate benchmark data.…”

Section: Introductionmentioning

confidence: 99%

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

Lutnæs

Teale

Helgaker

et al. 2009

The Journal of Chemical Physics

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121

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'Benchmarking density-functional-theory calculations of rotational g tensors and magnetizabilities using accurate coupled-cluster calculations. ', Journal of chemical physics., 131 (14 ). p. 144104.Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. An accurate set of benchmark rotational g tensors and magnetizabilities are calculated using coupled-cluster singles-doubles ͑CCSD͒ theory and coupled-cluster single-doubles-perturbative-triples ͓CCSD͑T͔͒ theory, in a variety of basis sets consisting of ͑rotational͒ 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 CCSD͑T͒ 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.

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Section: A Ensuring Gauge-origin Independencementioning

confidence: 99%

Section: B Comparison With Experimental Valuesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Lutnæs

Teale

Helgaker

et al. 2009

The Journal of Chemical Physics

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121

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“…The molecule has been placed in the yz-plane with the center of mass at the origin of the coordinates system and with the long axis of the molecule along the z axis. Due to the strong origin dependence observed for the conventional static magnetizability [23] when using a finite basis set, we have used London atomic orbitals (LAOs) [24] in the calculation of the conventional diamagnetic and paramagnetic contributions to the magnetizability [25,26]. The gauge-origin independence of the two expressions for the inverse permeability as well as of the electric permittivity has been verified by shifting the gauge origin.…”

Section: Computational Detailsmentioning

confidence: 99%

The origin dependence of the material constants: the permittivity and the inverse permeability

et al. 2015

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New derivations of origin-independent expressions for the electric permittivity are presented, starting either from the response function of the current density that defines the absorption coefficient, or from the off-resonance single-photon scattering amplitude that leads to the Kramers-Heisenberg dispersion formula. The resulting expression for the permittivity is compared with earlier work on the origin dependence of the material constants. Different origin-independent expressions for the permittivity, the inverse permeability and the magnetizability are calculated and discussed. By considering electromagnetic plane waves in the absence of external sources, the macroscopic Maxwell equations are used to describe the response of matter to external fields. In combination with the constitutive relations, a wave equation expressed in terms of the material constants is derived. It is shown that the different definitions of the material constants lead to the same wave equation. The non-uniqueness of the definitions of the material constants is discussed in this context. Finally, based on the discussions, we propose a possible unique, origin-independent definition of the material constants.

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“…13,29,30 DFT is particularly attractive because of its low computational cost. Recently, Wilson et al 30 presented an extensive assessment of DFT rotational g tensors, using a range of exchange-correlation functionals. They considered the local density approximation (LDA), the Becke-Lee-Yang-Parr (BLYP) 31 generalized gradient approximation (GGA), and the Becke-3-parameter-Lee-Yang-Parr (B3LYP) 32 hybrid functional.…”

Section: Introductionmentioning

confidence: 99%

Rotational g Tensors Calculated Using Hybrid Exchange-Correlation Functionals with the Optimized Effective Potential Approach

Teale

Helgaker

Tozer

2006

J. Chem. Theory Comput.

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Abstract:The calculation of rotational g tensors using density functional theory (DFT) with hybrid exchange-correlation functionals is considered. A total of 143 rotational g tensor elements in 58 molecules (67 isotopic combinations) are calculated using three standard hybrid functionals. Tensor elements determined using an uncoupled approach with orbitals and eigenvalues calculated from the multiplicative optimized effective potential (OEP) constitute a significant improvement over those determined in the conventional coupled manner with a nonmultiplicative exchange-correlation operator. Relative to experimental results, mean absolute errors are reduced by a factor of 2; mean errors and standard deviations are reduced by more than a factor of 3. The results are also an improvement over those determined using a generalized gradient-approximation functional optimized for magnetic response properties. The influence of orbital exchange is investigated for a representative subset of molecules, yielding an optimal amount near 0.3. Rotational g tensors are also determined from coupled-cluster electron densities using a combined DFT/wave-function approach. Being substantially more expensive, they do not offer a notable improvement on the pure DFT values from OEP-based hybrid calculations.

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The Rotational g Tensor as a Benchmark for Density-Functional Theory Calculations of Molecular Magnetic Properties

Cited by 30 publications

References 78 publications

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

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

The origin dependence of the material constants: the permittivity and the inverse permeability

Rotational g Tensors Calculated Using Hybrid Exchange-Correlation Functionals with the Optimized Effective Potential Approach

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