Gauge-origin independent calculations of Jones birefringence

We present the first gauge-origin independent formulation of Jones birefringence at the Hartree-Fock level of theory. Gauge-origin independence is achieved through the use of London atomic orbitals. The implementation is based on a recently proposed atomic orbital-based response theory formulation that allows for the use of both time- and perturbation-dependent basis sets [ Thorvaldsen , Ruud , Kristensen , Jørgensen , and Coriani , J. Chem. Phys. 129 , 214108 ( 2008 ) ]. We present the detailed expressions for the response functions entering the Jones birefringence when London atomic orbitals are used. The implementation is tested on a set of polar and dipolar molecules at the Hartree-Fock level of theory. It is demonstrated that London orbitals lead to much improved basis-set convergence, and that the use of small, conventional basis sets may lead to the wrong sign for the calculated birefringence. For large basis sets, London orbitals and conventional basis sets converge to the same results.