Chemical Shift and Shielding Calculations

 Subject: Chemical Shift and Shielding Calculations.
 Seiji Mori asked the following question:
 >   Dear Sirs,
 >
 >  I posted to CCL about the methods of NMR calculation a fey days ago , and
 > had an other question.
 > In G94, I tried to calculate the chemical shifts , there are magnetic
 > shieldings
 snip...
 > Would you please tell me the physical meaning of isotropic  and anitrosopy,
 > and which is an equivalent of the experimental chemical shift? It is better
 > that
 > you show the references.
 >
 >     Sincerely yours,
 >     Seiji Mori email:smori' at \`chem.s.u-tokyo.ac.jp
 The property calculated by an ab initio shielding scheme is typically a
 nuclear magnetic shielding tensor in the form of a 3x3 matrix. In
 physical terms the elements of the tensor represent the shielding along
 x,y and z when the applied magnetic field is along x,y and z in turn.
 This matrix may then be separated into symmetric and antisymmetric
 components, when the former is diagonalised then one obtains the three
 principal components of the shielding tensor denoted
 	sigma(1,1) sigma(2,2) and sigma(3,3)
 with the convention
 	sigma(3,3) >= sigma(2,2) >= sigma(1,1)
 the isotropic part of the shielding tensor is the trace or average of
 these three components and represents the value expected for an atom
 in a molecule that tumbles rapidly and isotropically.
 	trace = ( sigma(1,1) + sigma(2,2) + sigma(3,3)) /3
 In non isotropic
 systems such as single crystals or oriented liquid crystals the shielding
 takes on an orientational dependence. The shielding anisotropy is defined
 as
 	anisotropy = sigma(3,3) - ( sigma(1,1)+sigma(2,2) )/2
 and is a measure of the deviation of the shielding from spherical symmetry.
 For heavier nuclei the shielding anisotropy can be large (eg  > 5000 ppm
 in 199Hg and 205Tl compounds) and this can often be a significant
 mechanism for nuclear spin relaxation.
 In addition the shielding asymmetry may be defined as
 	asymmetry = (sigma(2,2)-sigma(1,1) ) / (sigma(3,3) -trace)
 An axially symmetric shielding tensor has a non zero anisotropy but a
 zero value for the asymmetry.
 The chemical shift measured by NMR is the difference between
 the shielding tensors for a nucleus in the compound under study and in the
 reference compound (typically TMS for 1H, 13C and 29Si). So to compare
 ab initio computed shielding with experimental chemical shifts two
 calculations will need to be performed one for the molecule under study
 and one for the reference compound. In addition experimental shifts are
 often found to be sensitive to environmental conditions such as solvent
 used, temperature, salt concentration etc. These are usually not taken
 into consideration in an ab initio calculation and so the comparison may
 only be valid if the intrinsic shift variations across a range of compounds
 far outweigh the environmental effects.
 No references to hand at the moment but I hope this helps.
 Best Wishes       __________________________________________________________
 Mark             /
          ___    /
         /  /|  /                     Mark J Forster
        /  / | /                     Biosym / Molecular Simulations.
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