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The Nuclear Shielding Surface: The Shielding as a Function of Molecular Geometry and Intermolecular Separation

  • Cynthia J. Jameson
  • Angel C. de Dios
Part of the NATO ASI Series book series (ASIC, volume 386)

Abstract

In making the connection between theoretical shielding values and experiments, it becomes necessary to consider medium effects and rovibrational averaging. The rovibrational averaging which takes the shielding for a molecule at its rigid equilibrium geometry into a thermal average shielding also provides the temperature dependence in the zero-pressure limit and the changes upon isotopic substitution which are experimentally accessible. The averaging of 15N and 31P shielding in the NH3 and PH3 molecules uses ab initio shielding surfaces and intramolecular potential surfaces or their derivatives. General trends are observed in comparing the shielding surfaces in these two molecules with H2O and CH4. A proper account of medium effects requires the knowledge of the intermolecular shielding surfaces, which are explored here for model systems 39Ar in Ar...Ar, Ar...Ne, Ar...Na+, Ar...NaH, and for 21Ne in Ne...Ne and Ne...He, employing ab initio calculations (LORG and SOLO). The shapes of the shielding function σ(R) for two atoms are shown to be similar for intra-and intermolecular shielding.

Keywords

Diatomic Molecule Isotope Shift Virial Coefficient Equilibrium Bond Length Intermolecular Separation 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer Science+Business Media Dordrecht 1993

Authors and Affiliations

  • Cynthia J. Jameson
    • 1
  • Angel C. de Dios
    • 2
  1. 1.Department of Chemistry M/C-111University of Illinois at ChicagoChicagoUSA
  2. 2.Department of ChemistryUniversity of Illinois at UrbanaUrbanaUSA

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