A fully analytical formulation is outlined for computing molecular magnetic susceptibilities and nuclear magnetic shieldings via a continuous change of origin of the electronic current density induced by an external magnetic field. The change of origin is described in terms of a (continuous) arbitrary shift function d(r). Coupled Hartree-Fock second-order magnetic properties of CH4 and CO2 molecules have been computed, using the special choice d(r) = r as generating function. A detailed analysis of results obtained with a variety of basis sets reveals that such a method is not as good as previously suggested. Large basis sets must be used to obtain accurate magnetic properties. On the other hand, all the components of theoretical nuclear magnetic shielding evaluated via this approach are independent of the origin of the vector potential. In general, theoretical magnetic susceptibilities depend linearly on the distance between different coordinate frames, but are origin independent for centre-symmetric molecules.
On Chf Calculations of 2nd-order Magnetic-properties Using the Method of Continuous Transformation of Origin of the Current-density
ZANASI, Riccardo
1994-01-01
Abstract
A fully analytical formulation is outlined for computing molecular magnetic susceptibilities and nuclear magnetic shieldings via a continuous change of origin of the electronic current density induced by an external magnetic field. The change of origin is described in terms of a (continuous) arbitrary shift function d(r). Coupled Hartree-Fock second-order magnetic properties of CH4 and CO2 molecules have been computed, using the special choice d(r) = r as generating function. A detailed analysis of results obtained with a variety of basis sets reveals that such a method is not as good as previously suggested. Large basis sets must be used to obtain accurate magnetic properties. On the other hand, all the components of theoretical nuclear magnetic shielding evaluated via this approach are independent of the origin of the vector potential. In general, theoretical magnetic susceptibilities depend linearly on the distance between different coordinate frames, but are origin independent for centre-symmetric molecules.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
