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

Bruno Senjean, Souloke Sen, Michal Repisky, Gerald Knizia, Lucas Visscher

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)1337-1354
Number of pages18
JournalJournal of Chemical Theory and Computation
Volume17
Issue number3
DOIs
StatePublished - Mar 9 2021

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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