Calculation of the electric hypershielding at the nuclei of molecules in a strong magnetic field

M. C. CAPUTO; M. B. FERRARO; G. I. PAGOLA; P. LAZZERETTI

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Año: 2007 vol. 126 p. 154103 - 154103

0021-9606

The third-rank electric hypershielding at the nuclei of 14 small molecules has been evaluated at the Hartree-Fock level of accuracy, by a pointwise procedure for the geometrical derivatives of magnetic susceptibilities and by a straightforward use of its definition within the Rayleigh-Schrodinger perturbation theory. The connection between these two quantities is provided by the Hellmann-Feynman theorem. The magnetically induced hypershielding at the nuclei accounts for distortion of molecular geometry caused by strong magnetic fields and for related changes of magnetic susceptibility. In homonuclear diatomics H2, N2, and F2, a field along the bond direction squeezes the electron cloud toward the center, determining shorter but stronger bond. It is shown that constraints for rotational and translational invariances and hypervirial theorems provide a natural criterion for Hartree-Fock quality of computed nuclear electric hypershielding.