Nuclear Magnetic Resonance Shielding Tensors Calculated with a Sum-over-States Density Functional Perturbation Theory

Malkin, Vladimir G.; Malkina, Olga L.; Casida, Mark E.; Salahub, Dennis R.

doi:10.1021/ja00092a046

Cited by 506 publications

(486 citation statements)

References 5 publications

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“…The deficiencies in the GGA-DFT NMR chemical shifts for nitrogen and oxygen [37][38][39][40] have been attributed to an insufficient separation between the occupied and virtual MOs, leading to excessively large paramagnetic contributions. We can take the HOMO-LUMO gap as a probe of the behavior of an approximate potential in the molecular region ͑as opposed to the asymptotic region͒, which will indicate whether the valence excitations in general will contribute more ͑smaller HOMO-LUMO gap͒ or less ͑larger gap͒ to the paramagnetic term.…”

Section: Resultsmentioning

confidence: 99%

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn–Sham density functional theory

Poater

Lenthe

Baerends

2003

The Journal of Chemical Physics

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In this paper, an orbital-dependent Kohn-Sham exchange-correlation potential, the so-called statistical average of ͑model͒ orbital potentials, is applied to the calculation of nuclear magnetic resonance chemical shifts of a series of simple molecules containing H, C, N, O, and F. It is shown that the use of this model potential leads to isotropic chemical shifts which are substantially improved over both local and gradient-corrected functionals, especially for nitrogen and oxygen atoms. This improvement in the chemical shift calculations can be attributed to the increase in the gap between highest occupied and lowest unoccupied orbitals, thus correcting the excessively large paramagnetic contributions, which have been identified to give deficient chemical shifts with both the local-density approximation and with gradient-corrected functionals. This is in keeping with the improvement by the statitical average of orbital model potentials for response properties in general and for excitation energies in particular. The present results are comparable in accuracy to those previously reported with self-interaction corrected functionals by Patchovskii et al., but still inferior to those obtained with accurate Kohn-Sham potentials by Wilson and Tozer. However, the present approach is computationally expedient and routinely applicable to all systems, requiring virtually the same computational effort as local-density and generalized-gradient calculations.

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Section: Resultsmentioning

confidence: 99%

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn–Sham density functional theory

Poater

Lenthe

Baerends

2003

The Journal of Chemical Physics

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“…3,16 By doing sum-over-states perturbation theory over the space of the Kohn-Sham orbitals, 5 we have derived theoretical expressions and implemented a computational algorithm to accurately predict the zero-field splittings of any inorganic or bioinorganic complex. As outlined by Pederson et al 6,7 and Malkin et al 5 the methodology is based on calculation of corrections to the nonrelativistic SDFT energies by incorporating the effects of spin-orbit coupling via sum-over-states second-order PT. The SOC operator can be written ͑in a.u.͒ as…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…Therefore, it has been of interest for several authors to develop and implement methodologies which take advantage of KS-SDFT in conjunction with perturbation theory ͑PT͒ to incorporate SOC, a relativistic effect. 5,6 Most notably, the pioneering work of Perderson et al 6,7 has paved the way for the computation of spinorbit effects on metal complexes.…”

Section: Introductionmentioning

confidence: 99%

First-principle computation of zero-field splittings: Application to a high valent Fe(IV)-oxo model of nonheme iron proteins

Aquino

Rodriguez

2005

The Journal of Chemical Physics

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We report the computational implementation of a combined spin-density-functional theory and perturbation theory ͑SDFT-PT͒ methodology for the accurate calculation of zero-field splittings ͑ZFS͒ in complexes of the most diverse nature including metal centers in proteins. We have applied the SDFT-PT methodology to study the cation of the recently synthesized complex ͓Fe IV ͑O͒-͑TMC͒͑NCCH 3 ͔͒͑OTf͒ 2 , ͓J. Rohde et al., Science 299, 1037 ͑2003͔͒ which is an important structural and functional analog of high-valent intermediates in catalytic cycles of nonheme iron enzymes. The calculated value ͑D Theory = 28.67 cm −1 ͒ is in excellent agreement with the unusually large ZFS reported by experiment ͑D Exp =29±3 cm −1 ͒. The principal component D zz of the ZFS tensor is oriented along the Fe IV = oxo bond indicating that the oxo ligand dominates the electronic structure of the complex.

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“…Other investigations on molecular systems have shown that calculated shielding parameters are highly dependant on the type of XC functionals. [106][107][108][109][110] Linear response of crystalline or molecular orbitals to the magnetic field perturbation are strongly dependant on the occupied-virtual energy gap (E gap ) and the shape of the virtual orbitals, through the first-order corrected wave function (Eq. 14).…”

Section: B Improvement Of Dft Calculationsmentioning

confidence: 99%

Density functional theory investigation of3dtransition metal NMR shielding tensors in diamagnetic systems using the gauge-including projector augmented-wave method

2007

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Nuclear Magnetic Resonance Shielding Tensors Calculated with a Sum-over-States Density Functional Perturbation Theory

Cited by 506 publications

References 5 publications

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn–Sham density functional theory

Nuclear magnetic resonance chemical shifts with the statistical average of orbital-dependent model potentials in Kohn–Sham density functional theory

First-principle computation of zero-field splittings: Application to a high valent Fe(IV)-oxo model of nonheme iron proteins

Density functional theory investigation of3dtransition metal NMR shielding tensors in diamagnetic systems using the gauge-including projector augmented-wave method

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