On the Origin of <sup>35/37</sup>Cl Isotope Effects on <sup>195</sup>Pt NMR Chemical Shifts. A Density Functional Study

Davis, Jeffrey R.; Bühl, Michæl; Koch, Klaus

doi:10.1021/ct300105q

Cited by 21 publications

(74 citation statements)

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“…As found for the aquo complexes in the previous paper, however, 24 there are quantitative discrepancies, apparent in a noticeable scatter of the data and a typically overestimated slope of the  calc vs.  exp data. It is unclear at present whether these discrepancies are due to residual numerical errors in the computations, deficiencies of the overall model (e.g.…”

Section: /37mentioning

confidence: 56%

“…The same protocol as in our previous study 24 32,33,34 elsewhere. This combination of functional and basis sets has performed very well for the description of bond distances between third-row transition metals and their ligands.…”

Section: Computational Detailsmentioning

confidence: 99%

“…In our previous paper 24 we have calculated such zero-point corrections to the gas- complexes, large solvation effects were apparent, but were found difficult to include at present. 24 It is known that immersion in a polar solvent can reinforce metal-water bonds, probably due to cooperative polarization effects.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the protocol for the gas-phase calculations presented previously 24 , could still be a good approximation to the situation in solution, if effective error cancelation occurs, a possibility that will be explored in the present paper. 6−n ] 3−n (n = 3-6) complexes in equilibrated hydrochloric acid solutions, are also well-resolved into a distinctive fine-structure due to 35 Cl/ 37 Cl isotopologue and isotopomer effects, resulting in a unique NMR finger-print.…”

Section: Introductionmentioning

confidence: 99%

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Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory

2013

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Section: /37mentioning

confidence: 56%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory

2013

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“…In conjunction with density functional theory (DFT), ZORA is widely applied to calculations of NMR parameters. For a small selection of recent applications to a variety of problems in chemistry see, for instance [11][12][13][14][15][16]. A ZORA module for NMR shielding tensors has been part of the Amsterdam Density Functional (ADF) [17] package since 1999 [18,19], followed by an implementation of a module for calculations of indirect nuclear spin-spin coupling (J-coupling) tensors in the year 2000 [20,21].…”

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The role of the exchange-correlation response kernel and scaling corrections in relativistic density functional nuclear magnetic shielding calculations with the zeroth-order regular approximation

Autschbach

2013

Molecular Physics

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To cite this article: Jochen Autschbach (2013) The role of the exchange-correlation response kernel and scaling corrections in relativistic density functional nuclear magnetic shielding calculations with the zeroth-order regular approximation,The relativistic NMR module of the Amsterdam Density Functional (ADF) package, which is frequently utilised in studies of heavy atom NMR chemical shifts, is extended to calculate a hitherto neglected term from the response of the exchangecorrelation (XC) potential. The term vanishes in the absence of spin-orbit coupling. Further, corrections to the shielding arising from scaling factors in the zeroth-order regular approximation (ZORA) relativistic framework are investigated. The XC response markedly improves calculated proton chemical shifts for hydrogen halides. Mercury chemical shifts for mercury dihalides are also noticeably altered. Contributions from density-gradient dependent terms in the response kernel contribute about 30-40%. New fully relativistic density functional theory (DFT) benchmark data are compared with ZORA and literature reference values. In line with previous work, it is found that absolute shielding constants for Hg are not accurately predicted with ZORA. However, chemical shifts agree well with fully relativistic calculations. The application of 'scaled-ZORA' scaling factors deteriorates the shielding constants and is therefore not recommended. The scaling hardly affects chemical shifts. ZORA calculations are not suitable for absolute shielding of heavy atoms but they can be used safely for chemical shifts in most application scenarios. IntroductionFirst-principles calculations of structure, thermochemistry, and spectroscopic properties of molecules with heavy elements require a relativistic quantum chemistry framework [1][2][3][4][5][6][7]. This is particularly true for molecular properties for which the relevant quantum mechanical operators predominantly sample the electronic structure close to a nucleus. NMR parameters are prime examples of such properties. The zeroth-order regular approximation (ZORA) [8-10] is a variationally stable approximate (quasirelativistic) twocomponent (2c) all-electron relativistic framework. In conjunction with density functional theory (DFT), ZORA is widely applied to calculations of NMR parameters. For a small selection of recent applications to a variety of problems in chemistry see, for instance [11][12][13][14][15][16]. A ZORA module for NMR shielding tensors has been part of the Amsterdam Density Functional (ADF) [17] package since 1999 [18,19], followed by an implementation of a module for calculations of indirect nuclear spin-spin coupling (J-coupling) tensors in the year 2000 [20,21]. Among the reasons for the early development of ZORA-based magnetic property modules have been the ease by which magnetic perturbation operators can be derived and the rather straightforward way of calculating matrix elements with the help of numerical integration techniques. Extensions for hybrid DFT calculations have been

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CalculatingNMRChemical Shifts andJ‐Couplings for Heavy Element Compounds

Autschbach

2014

Encyclopedia of Analytical Chemistry

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Ab initio calculations of NMR parameters for compounds with heavy elements require a relativistic theoretical framework. Such calculations are able to reproduce experimentally observed ‘heavy atom’ effects in NMR spectroscopy quantitatively. Electron spin‐orbit (SO) coupling is a relativistic effect that leads to the ‘normal halogen dependence’ of light atom chemical shifts in the vicinity of heavy halogens. Similar effects exist for light atoms bound to heavy transition metals or f ‐block elements or heavy main group elements other than halogens. J ‐coupling constants involving heavy elements may increase by several hundred percent because of relativistic effects. The tensor properties of NMR shielding and J ‐coupling, observed routinely in solid‐state NMR, can be impacted very strongly by relativistic effects. This article discusses representative examples, provides a rationale why relativistic effects are large for atoms with high nuclear charges, and lists a selection of quantum chemistry program packages that are capable of relativistic NMR calculations.

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On the Origin of ^35/37Cl Isotope Effects on ¹⁹⁵Pt NMR Chemical Shifts. A Density Functional Study

Cited by 21 publications

References 44 publications

Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory

Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory

The role of the exchange-correlation response kernel and scaling corrections in relativistic density functional nuclear magnetic shielding calculations with the zeroth-order regular approximation

CalculatingNMRChemical Shifts andJ‐Couplings for Heavy Element Compounds

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On the Origin of 35/37Cl Isotope Effects on 195Pt NMR Chemical Shifts. A Density Functional Study

Cited by 21 publications

References 44 publications

Probing Isotope Shifts in 103Rh and 195Pt NMR Spectra with Density Functional Theory

Probing Isotope Shifts in 103Rh and 195Pt NMR Spectra with Density Functional Theory

The role of the exchange-correlation response kernel and scaling corrections in relativistic density functional nuclear magnetic shielding calculations with the zeroth-order regular approximation

CalculatingNMRChemical Shifts andJ‐Couplings for Heavy Element Compounds

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On the Origin of ^35/37Cl Isotope Effects on ¹⁹⁵Pt NMR Chemical Shifts. A Density Functional Study

Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory

Probing Isotope Shifts in ¹⁰³Rh and ¹⁹⁵Pt NMR Spectra with Density Functional Theory