Theory of magnetic susceptibilities and NMR chemical shifts in terms of localized quantities. II. Application to some simple molecules

Schindler, Michael; Kutzelnigg, Werner

doi:10.1063/1.443165

Cited by 647 publications

(323 citation statements)

References 61 publications

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“…MOs of oxygen and sulfur make a shielding contribution in this direction. It should be mentioned that similar findings were previously reported by Schindler and Kutzelnigg from an IGLO calculation on formaldehyde (38). However, it is interesting that the lone pair MOs are predicted to make the largest contribution to the decreased shielding observed for 6,, in thioacetamide relative to acetamide.…”

Section: (B) Carbon Chemical Shielding Tensor Calculationssupporting

confidence: 85%

A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

Kirby¹,

Lumsden²,

Wasylishen³

1995

Can. J. Chem.

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The carbon chemical shift tensors of the carbonyl and thiocarbonyl groups of acetamide, thioacetamide, thioacetanilide, 4'-methoxyacetanilide, and 4'-methoxythioacetanilide have been experimentally determined using dipolar -chemical shift solid-state 13c NMR spectroscopy. The magnitudes of the three principal components of the carbon chemical shift tensors are found to exhibit marked variations between the carbonyl and thiocarbonyl functionalities. However, in contrast to the conclusions of an earlier comparative investigation involving benzophenone and thiobenzophenone, the orientations of the principal axis systems of these chemical shift tensors are found to be similar. These experimental results represent the first complete characterizations of the carbon chemical shift tensor in organic thiocarbonyls. The results of our ab initio GIAO and LORG calculations of carbon chemical shielding tensors in formaldehyde, thiofomaldehyde, formamide, and thioformamide as well as in acetamide and thioacetamide are in qualitative agreement with experiment. The findings of the present investigation provide conclusive evidence that the well-known isotropic deshielding of the carbon nucleus in the C=S group relative to C=O is primarily attributable to the decreased energy associated with the o tt T* excitation within the thiocarbonyl fragment. This result is in contrast with the conventional interpretation that the deshielding originates from a red shift in the C=S HOMO-LUMO n + T* transition.Key words: chemical shift tensors, solid-state I3C NMR, carbonyls, thiocarbonyls, ab initio calculations.RksumC : Utilisant les deplacements chimiques dipolaires de la spectroscopie RMN du I3c 2i I'ttat solide, on a determine exptrimentalement les tenseurs des dtplacements chimiques du carbone des groupes carbonyle et thiocarbonyle des acttamide, thioacetamide, thioacttanilide, 4'-mCthoxyacCtanilide et 4'-mCthoxythioacttanilide. On a trouvt que les amplitudes des trois principales composantes des tenseurs des dtplacements chimiques du carbone presentent des variations importantes entre les fonctions carbonyles et thiocarbonyles. Toutefois, en opposition avec les conclusions tirkes 2i partir d'une ttude comparative anttrieure impliquant la benzophenone et la thiobenzophtnone, on a trouvt que les orientations des principaux axes de rtftrence de ces tenseurs des dCsplacements chimiques sont semblables. Ces resultats exptrimentaux representent les premihres caractkrisations complktes du tenseur du dtplacement chimique des thiocarbonyles organiques. Les rtsultats de nos calculs ab initio GIAO et LORG des tenseurs d'tcran chimique du carbone dans les formaldthyde, thiofomaldChyde, formamide, thiofomamide ainsi qu'acttamide et thioacttamide sont en accord qualitatif avec les rtsultats expCrimentaux. Les observations faites dans le present travail fournissent des bases concluantes qui permettent d'attribuer le deblindage bien connu du noyau du carbone dans le groupe C=S par rapport au C=O 2i une diminution de l'energie associee B une e...

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Section: (B) Carbon Chemical Shielding Tensor Calculationssupporting

confidence: 85%

A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

Kirby¹,

Lumsden²,

Wasylishen³

1995

Can. J. Chem.

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“…Chemical shielding constants were calculated using the IGLO technique [16,17] as implemented in the dEMON-NMR package [18,19]. An IGLO-III basis set [20] was chosen for all following calculations.…”

Section: Benchmark Calculationsmentioning

confidence: 99%

29Si NMR chemical shifts of silane derivatives

Corminbœuf¹,

Heine²,

Weber³

2002

Chemical Physics Letters

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“…The calculation of nuclear magnetic (NMR) shielding constants represents an example of a molecular property that requires a good representation of the orbitals near the nuclei, and basis sets have been designed for the calculation of NMR properties. For example, the individual gauge for localised orbitals (IGLO) basis sets [42,43] are often used for the calculation of magnetic properties; however, they have only been defined for hydrogen and the first-and second-row p-block elements. A family of segmented contracted basis sets, denoted pcSseg-n, optimised for the calculation of nuclear magnetic shielding constants has also been reported [44].…”

Section: Introductionmentioning

confidence: 99%

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

Fouda

Besley

2017

Theor Chem Acc

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The performance of Gaussian basis sets for density functional theory-based calculations of core-electron spectroscopies is assessed. The convergence of core-electron binding energies and core-excitation energies using a range of basis sets including split-valence, correlation-consistent, polarisation-consistent and individual gauge for localised orbitals basis sets is studied. For self-consistent field calculations of core-electron binding energies and core-excitation energies of first-row elements, relatively small basis sets can accurately reproduce the values of much larger basis sets, with the IGLO basis sets performing particularly well. Calculations for the K-edge of second-row elements are more challenging, and of the smaller basis sets, pcSseg-2 has the best performance. For the correlation-consistent basis sets, inclusion of core-valence correlation functions is important, with the cc-pCVTZ basis set giving accurate results. Time-dependent density functional theory-based calculations of core-excitation energies show less sensitivity to the basis set with relatively small basis sets, such as pcSseg-1 or pcSseg-2, reproducing the values for much larger basis sets accurately. In contrast, time-dependent density functional theory calculations of X-ray emission energies are highly dependent on the basis set, but the IGLO-II, IGLO-III and pcSseg-2 basis sets provide a good level of accuracy.

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Theory of magnetic susceptibilities and NMR chemical shifts in terms of localized quantities. II. Application to some simple molecules

Cited by 647 publications

References 61 publications

A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

29Si NMR chemical shifts of silane derivatives

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

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Theory of magnetic susceptibilities and NMR chemical shifts in terms of localized quantities. II. Application to some simple molecules

Cited by 647 publications

References 61 publications

A solid-state 13C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

A solid-state 13C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

29Si NMR chemical shifts of silane derivatives

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

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Product

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A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors

A solid-state ¹³C NMR and theoretical investigation of carbonyl and thiocarbonyl carbon chemical shift tensors