The Rotational g Tensor as a Benchmark for Ab Initio Molecular Property Calculations

Mohn, Chris E.; Wilson, David J.; Lutnæs, Ola B.; Helgaker, Trygve; Ruud, Kenneth

doi:10.1016/s0065-3276(05)50005-4

Cited by 8 publications

(18 citation statements)

References 48 publications

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“…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.…”

Section: B Comparison With Experimental Valuesmentioning

confidence: 99%

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: B Comparison With Experimental Valuesmentioning

confidence: 99%

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

Self Cite

121

View full text Add to dashboard Cite

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“…Moreover, its rotational g tensor is particularly sensitive to changes in the geometry. 49 We note that the magnitude of the largest component of the g tensor is very large compared to the average range of valuesssee Figure 2, where the experimental principal g xx element of O 3 lies well outside the typical range of values. For these reasons, we have listed the ozone g tensor elements separately in Table 4.…”

Section: Comparison With Experimentsmentioning

confidence: 64%

“…In a previous MCSCF study of ozone, the zero-point vibrational corrections were found to be -0.0707 (g xx ), -0.0018 (g yy ), and -0.0014 (g zz ). 49 For the principal g xx component, therefore, the inclusion of vibrational corrections worsens the agreement with experiment, for all methods. Moreover, for the g zz component, only the Hartree-Fock result is closer to experimental results with the inclusion of vibrational corrections, whereas for the g yy component, only the KT2 and KT3 functional results are closer to experimental results.…”

Section: Comparison With Experimentsmentioning

confidence: 93%

“…Geometry Dependence. It has been shown previously 49 that calculated rotational g tensors are sensitive to molecular geometry, necessitating the use of accurate molecular geometries. To illustrate this dependence, the significant deviations between the calculated g tensor elements of glycoaldehyde and methyl formate in Table 7 may be attributed to geometry effects, with tensor elements calculated at the experimental geometries typically within 0.005 of experimental results, in contrast to the deviations of greater than 0.2 for the principal g-tensor component of glycoaldehyde.…”

Section: Comparison With Experimentsmentioning

confidence: 99%

“…5 To date, very few DFT studies of rotational g tensors have been reported, 48 only one of which (from our laboratory) uses London orbitals. 49 Here, we present London DFT calculations of the rotational g tensor for the 61 organic molecules listed in Table 1. These molecules differ in the importance and relative magnitudes of static and dynamic electron correlation; hence, they constitute a suitable set for testing the accuracy of various computational approaches in the calculation of g tensors.…”

Section: Introductionmentioning

confidence: 99%

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

Wilson

Mohn

Helgaker

2005

J. Chem. Theory Comput.

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Abstract:The rotational g factor for a large number of organic compounds has been investigated with density-functional theory. Rapid convergence toward the basis-set limit is ensured by the use of London atomic orbitals. A statistical analysis of the results has been carried out in comparison with accurate experimental data. It is shown that gradient-corrected and hybrid functionals reproduce experimental results most closely, with the Keal-Tozer KT2 functional being the most accurate.

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Global Analytical Potential Energy Surfaces for High‐resolution Molecular Spectroscopy and Reaction Dynamics

Marquardt¹,

Qüack²

2011

Handbook of High‐resolution Spectroscopy

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Analytical representations of potential energy hypersurfaces for the nuclear motion in polyatomic molecules from ab initio theory and experiment are discussed in a general way. The qualification of potential hypersurface representations from ab initio theory regarding the description of experimental data from rovibrational high-resolution spectroscopy and chemical reaction kinetics is analyzed in more detail for a restricted group of molecules including methane, CH 4 , ammonia, NH 3 , H 2 O 2 , and (HF) 2 . Current methods for the derivation of analytical representations of potential energy surfaces as well as some applications are reviewed.

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The Rotational g Tensor as a Benchmark for Ab Initio Molecular Property Calculations

Cited by 8 publications

References 48 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 Rotational g Tensor as a Benchmark for Density-Functional Theory Calculations of Molecular Magnetic Properties

Global Analytical Potential Energy Surfaces for High‐resolution Molecular Spectroscopy and Reaction Dynamics

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