Fully relativistic calculation of nuclear magnetic shieldings and indirect nuclear spinspin couplings in group15 and 16 hydrides
Abstract
Fully relativistic calculations of the isotropic and anisotropic parts of both indirect nuclear spinspin couplings ^{1}J(XH) and ^{2}J(HH) and nuclear magnetic shieldings σ(X) and σ(H) for the group15 and 16 hydrides are presented. Relativistic calculations were performed with DiracFock wave functions and the random phase approximation method. Results are compared to its nonrelativistic counterpart. Paramagnetic and diamagnetic contributions to the nuclear magnetic shielding constants are also reported. We found very large relativistic corrections to both properties in the sixthrow hydrides (BiH_{3} and PoH_{2}). Our calculations of the relativistic corrections to the isotropic part of σ at the heavy nucleus X show that it is roughly proportional to Z^{3.2} in both series of molecules. Paramagnetic term σ^{p} is more sensitive to the effects of relativity than the diamagnetic one σ^{d}, even though both have a behavior proportional to third power of the nuclear charge Z.
 Publication:

Journal of Chemical Physics
 Pub Date:
 November 2002
 DOI:
 10.1063/1.1510731
 Bibcode:
 2002JChPh.117.7942G
 Keywords:

 Correction;
 Nuclear Magnetic Resonance;
 Relativistic Effects;
 SpinSpin Coupling;
 33.25.+k;
 31.30.Jv;
 Atomic and Molecular Physics;
 Nuclear resonance and relaxation;
 Relativistic and quantum electrodynamic effects in atoms and molecules