Origin Invariant Full Optical Rotation Tensor in the Length Dipole Gauge without London Atomic Orbitals

Abstract

\n \n \n We present an origin-invariant approach to compute the full optical rotation tensor (Buckingham/Dunn\ntensor) in the length dipole gauge without recourse to London atomic orbitals, called LG(OI). The LG(OI)\napproach is simpler and less computationally demanding than the more common LG-London and modified\nvelocity gauge (MVG) approaches and it can be used with any approximate wave function or density functional\nmethod. We report an implementation at coupled cluster with single and double excitations level (CCSD), for\nwhich we present the first simulations of the origin-invariant Buckingham/Dunn tensor in the length gauge.\nWith this method, we attempt to decouple the effects of electron correlation and basis set incompleteness on\nthe choice of gauge for optical rotation calculations on simple test systems. The simulations show a smooth\nconvergence of the LG(OI) and MVG results with the basis set size towards the complete basis set limit.\nHowever, these preliminary results indicate that CCSD may not be close to a complete description of the\nelectron correlation effects on this property even for small molecules, and that basis set incompleteness may\nbe a less important cause of discrepancy between choices of gauge than electron correlation incompleteness.\n\n \n \n