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We present an origin-invariant approach to compute the full optical rotation tensor (Buckingham/Dunn tensor) in the length dipole gauge without recourse to London atomic orbitals, called LG(OI). The LG(OI) approach is simpler and less computationally demanding than the more common length gauge (LG)-London and modified velocity gauge (MVG) approaches, and it can be used with any approximate wave function or density functional method. We report an implementation at the coupled cluster with single and double excitations level (CCSD), for which we present the first simulations of the origin-invariant Buckingham/Dunn tensor in the LG. We compare LG(OI) and MVG results on a series of 22 organic molecules, showing good linear correlation between the approaches, although for small tensor elements, they provide values of opposite sign. We also attempt to decouple the effects of electron correlation and basis set incompleteness on the choice of gauge for specific rotation calculations on simple test systems. The simulations show a smooth convergence of the LG(OI) and MVG results with the basis set size toward the complete basis set limit. However, these preliminary results indicate that CCSD may not be close to a complete description of the electron correlation effects on this property even for small molecules and that basis set incompleteness may be a less important cause of discrepancy between choices of gauge than electron correlation incompleteness. [ABSTRACT FROM AUTHOR]

We present an approach to perform origin invariant optical rotation calculations in the length dipole gauge without recourse to London atomic orbitals, called origin invariant length gauge [LG(OI)]. The LG(OI) approach works with any approximate wave function or density functional method, but here we focus on the implementation with the coupled cluster (CC) with single and double excitations method because of the lack of production-level alternatives. Preliminary numerical tests show the efficacy of the LG(OI) procedure and indicate that putting the origin in the center of mass of a molecule may not be an optimal choice for conventional CC-LG calculations. [ABSTRACT FROM AUTHOR]