Generalization of Intrinsic Orbitals to Kramers-Paired Quaternion Spinors, Molecular Fragments, and Valence Virtual Spinors

Localization of molecular orbitals finds its importance in the representation of chemical bonding (and antibonding) and in the local correlation treatments beyond mean-field approximation. In this paper, we generalize the intrinsic atomic and bonding orbitals [G. Knizia, J. Chem. Theory Comput. 2013, 9, 11, 4834-4843] to relativistic applications using complex and quaternion spinors, as well as to molecular fragments instead of atomic fragments only. By performing a singular value decomposition, we show how localized valence virtual orbitals can be expressed on this intrinsic minimal basis. We demonstrate our method on systems of increasing complexity, starting from simple cases such as benzene, acrylic acid, and ferrocene molecules, and then demonstrate the use of molecular fragments and inclusion of relativistic effects for complexes containing heavy elements such as tellurium, iridium, and astatine. The aforementioned scheme is implemented into a standalone program interfaced with several different quantum chemistry packages.

Automated summary

Localization of molecular orbitals is important in representing chemical bonding and in local correlation treatments beyond mean-field approximation. This paper generalizes intrinsic atomic and bonding orbitals to relativistic applications using complex and quaternion spinors, as well as incorporating molecular fragments. By performing a singular value decomposition, the method shows how localized valence virtual orbitals can be expressed on an intrinsic minimal basis. The developed scheme is implemented into a standalone program interfaced with various quantum chemistry packages, demonstrating its applicability on systems of increasing complexity.