Electron-correlated calculations, nuclear shifts

J. Gauss, Effects of electron correlation in the calculation of nuclear magnetic resonance chemical shifts, J. Chem. Phys. 99 (1993) 3629. 

Second-Order Many-Body Perturbation Theory Using Gauge-Including Atomic Orbitals. J. Gauss,/. Chem. Phys, 99, 3629 (1993). Effects of Electron Correlation in the Calculation of Nuclear Magnetic Resonance Chemical Shifts. 

Also in 2-substituted ethanesulphonates,35 the 33S chemical shift has a reverse substituent effect and correlates with both Taft substituent constants and the chemical shift of the carboxylic carbon in related carboxylic acids. It seems that the substituent effect does not depend on conformation, but prevailingly on intramolecular electronic effects. Density functional theory (DFT) calculations of 33S nuclear shielding constants and natural bond orbital (NBO) analysis made it possible to conclude that substituents cause a variation in the polarization of the S-C and S-O bonds and of the oxygen lone pairs of the C — S03 moiety. This affects the electron density in the surroundings of the sulphur nucleus and consequently the expansion or contraction of 3p sulphur orbitals. 

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