Although electrodynamics is formally invariant in a gauge transformation, the values of some physical quantities, e.g., magnetic properties, depend on the approximation employed to calculate them. The conditions for gauge independence of third-rank tensor properties that describe the response of a molecule in the presence of three perturbations, that is, external electric and magnetic field, and intramolecular nuclear magnetic dipoles, are discussed. The relationships for invariance of the physical properties to a gauge translation are exactly the same as the constraints for charge conservation. They are expressed in terms of second-rank response properties, namely electric polarizabilities and electric shielding at the nuclei. An extended numerical test has been carried out to determine the Hartree-Fock limit for a series of quantities entering the gauge-invariance sum rules.
Sum rules related to third-order properties: a numerical check / Caputo, Mc; Lazzeretti, Paolo. - In: CHEMICAL PHYSICS. - ISSN 0301-0104. - STAMPA. - 288:2-3(2003), pp. 281-289. [10.1016/S0301-0104(03)00033-8]
Sum rules related to third-order properties: a numerical check
LAZZERETTI, Paolo
2003
Abstract
Although electrodynamics is formally invariant in a gauge transformation, the values of some physical quantities, e.g., magnetic properties, depend on the approximation employed to calculate them. The conditions for gauge independence of third-rank tensor properties that describe the response of a molecule in the presence of three perturbations, that is, external electric and magnetic field, and intramolecular nuclear magnetic dipoles, are discussed. The relationships for invariance of the physical properties to a gauge translation are exactly the same as the constraints for charge conservation. They are expressed in terms of second-rank response properties, namely electric polarizabilities and electric shielding at the nuclei. An extended numerical test has been carried out to determine the Hartree-Fock limit for a series of quantities entering the gauge-invariance sum rules.Pubblicazioni consigliate
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