Calculation of nuclear magnetic shieldings using an analytically differentiated relativistic shielding formula.

Two expressions for nuclear-magnetic-shielding tensor components based on analytically differentiating the electronic energy of a system are presented. The first is based on a second-order Douglas-Kroll-Hess approach, in which the off-diagonal block terms of the transformed Dirac Hamiltonian are diminished to second order with respect to both the electrostatic nuclear attraction potential V and the magnetic vector potential A. The second expression is based on the method of Barysz-Sadlej-Snijders, in which the off-diagonal block terms in the transformed Dirac Hamiltonian are completely eliminated with respect to purely V terms, while they are diminished to second order with respect to terms including A. The two approaches are applied to the calculation of nuclear magnetic shieldings of HX (X=F,Cl,Br,I), H2X (X=O,S,Se,Te), and noble gas X (X=He,Ne,Ar,Kr,Xe) systems with common gauge origins. The results show that relativistic corrections of higher than second order are negligibly small, except for the paramagnetic parts of I, Te, and Xe shieldings. The present calculations yield very large positive values for the anisotropy of proton shielding, Δσ(H)=σ∥(H)-σ⊥(H), of HI compared to previous reports. Unfortunately, no experimental values for the anisotropy of proton shielding in HI are available for verification. [ABSTRACT FROM AUTHOR]