Exploitation of complex Abelian point groups in quantum-chemical calculations

Abstract

Quantum-chemical calculations often make use of point-group theory to exploit molecular symmetry, resulting in a reduction of the computational cost and in insights into the electronic structure. This exploitation is often limited to subgroups of $D_{2h}$ which are Abelian with real characters. Here, we extend the symmetry exploitation to Abelian point groups with complex characters. Such point groups are often encountered in calculations that involve finite magnetic fields, though their occurrence is not limited to these cases alone. We present the evaluation of integrals over symmetry-adapted orbitals using the double-coset decomposition, as well as the use of these symmetries in the contractions needed within post Hartree Fock calculations in the context of block tensors. Efficiency gains are discussed for four simple hydrocarbons that exhibit a complex Abelian point group in the presence of a magnetic field.