On the origin independence of the Verdet tensor

The condition for invariance under a translation of the coordinate system of the Verdet tensor and the Verdet constant, calculated via quantum chemical methods using gaugeless basis sets, is expressed by a vanishing sum rule involving a third-rank polar tensor. The sum rule is, in principle, satisfied only in the ideal case of optimal variational electronic wavefunctions. In general, it is not fulfilled in non-variational calculations and variational calculations allowing for the algebraic approximation, but it can be satisfied for reasons of molecular symmetry. Group-theoretical procedures have been used to determine (i) the total number of non-vanishing components and (ii) the unique components of both the polar tensor appearing in the sum rule and the axial Verdet tensor, for a series of symmetry groups. Test calculations at the random-phase approximation level of accuracy for water, hydrogen peroxide and ammonia molecules, using basis sets of increasing quality, show a smooth convergence to zero of the sum rule. Verdet tensor components calculated for the same molecules converge to limit values, estimated via large basis sets of gaugeless Gaussian functions and London orbitals.Fil: Caputo, Maria Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires; Argentina; Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Física; Argentina;Fil: Coriani, S.. Universita degli Studi di Trieste. Dipartimento di Scienze Chimiche e Farmaceutiche; Italia;Fil: Pelloni, S.. Universita degli Studi di Modena e Reggio Emilia. Dipartimento di Scienze Chimiche e Geologiche; Italia;Fil: Lazzeretti, P.. Universita degli Studi di Modena e Reggio Emilia. Dipartimento di Scienze Chimiche e Geologiche; Italia