14N quadrupolar, 14N and 15N chemical shift, and 14N-1H dipolar tensors of sulfamic acid

Gerard S. Harbison, Young Sik Kye, Glenn H. Penner, Michelle Grandin, Martine Monette

Research output: Contribution to journalArticle

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Abstract

A 14N solid-state NMR single crystal study was used to determine the 14N quadrupolar, chemical shift, and 14N-1H dipolar tensors of sulfamic acid. The quadrupolar tensor is nearly axially symmetric, with the quasiunique axis aligned 3° away from the N-S bond. The quadrupole coupling constant of 0.794 MHz is substantially less than the gas-phase value (1.6682 MHz); ab initio calculations show that the difference can be attributed almost entirely to the significantly shorter N-S bond in the solid state. The single crystal study, together with 15N CP/MAS and CP/static experiments, yields an isotropic chemical shift that lies close to its solution value, and a chemical shielding anisotropy of about -80 ppm, and the dipolar couplings are about 10% smaller than computed from the neutron structure, probably because of vibrational averaging. All three tensors are almost collinear. HF, MP2, CI, and DFT(B3LYP) calculations of the nitrogen quadrupole coupling constant and shielding are also reported.

Original languageEnglish (US)
Pages (from-to)10285-10291
Number of pages7
JournalJournal of Physical Chemistry B
Volume106
Issue number40
DOIs
StatePublished - Oct 10 2002

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Sulfamic acid
Chemical shift
Tensors
chemical equilibrium
tensors
Shielding
acids
shielding
quadrupoles
Single crystals
solid state
single crystals
Discrete Fourier transforms
Neutrons
Anisotropy
Nitrogen
Gases
Nuclear magnetic resonance
vapor phases
nitrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

14N quadrupolar, 14N and 15N chemical shift, and 14N-1H dipolar tensors of sulfamic acid. / Harbison, Gerard S.; Kye, Young Sik; Penner, Glenn H.; Grandin, Michelle; Monette, Martine.

In: Journal of Physical Chemistry B, Vol. 106, No. 40, 10.10.2002, p. 10285-10291.

Research output: Contribution to journalArticle

Harbison, Gerard S. ; Kye, Young Sik ; Penner, Glenn H. ; Grandin, Michelle ; Monette, Martine. / 14N quadrupolar, 14N and 15N chemical shift, and 14N-1H dipolar tensors of sulfamic acid. In: Journal of Physical Chemistry B. 2002 ; Vol. 106, No. 40. pp. 10285-10291.
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AU - Monette, Martine

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N2 - A 14N solid-state NMR single crystal study was used to determine the 14N quadrupolar, chemical shift, and 14N-1H dipolar tensors of sulfamic acid. The quadrupolar tensor is nearly axially symmetric, with the quasiunique axis aligned 3° away from the N-S bond. The quadrupole coupling constant of 0.794 MHz is substantially less than the gas-phase value (1.6682 MHz); ab initio calculations show that the difference can be attributed almost entirely to the significantly shorter N-S bond in the solid state. The single crystal study, together with 15N CP/MAS and CP/static experiments, yields an isotropic chemical shift that lies close to its solution value, and a chemical shielding anisotropy of about -80 ppm, and the dipolar couplings are about 10% smaller than computed from the neutron structure, probably because of vibrational averaging. All three tensors are almost collinear. HF, MP2, CI, and DFT(B3LYP) calculations of the nitrogen quadrupole coupling constant and shielding are also reported.

AB - A 14N solid-state NMR single crystal study was used to determine the 14N quadrupolar, chemical shift, and 14N-1H dipolar tensors of sulfamic acid. The quadrupolar tensor is nearly axially symmetric, with the quasiunique axis aligned 3° away from the N-S bond. The quadrupole coupling constant of 0.794 MHz is substantially less than the gas-phase value (1.6682 MHz); ab initio calculations show that the difference can be attributed almost entirely to the significantly shorter N-S bond in the solid state. The single crystal study, together with 15N CP/MAS and CP/static experiments, yields an isotropic chemical shift that lies close to its solution value, and a chemical shielding anisotropy of about -80 ppm, and the dipolar couplings are about 10% smaller than computed from the neutron structure, probably because of vibrational averaging. All three tensors are almost collinear. HF, MP2, CI, and DFT(B3LYP) calculations of the nitrogen quadrupole coupling constant and shielding are also reported.

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