Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals

Elvira R. Sayfutyarova, Qiming Sun, Garnet Kin Lic Chan, Gerald Knizia

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

We introduce the atomic valence active space (AVAS), a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference (MR) electronic structure calculations. Concretely, the technique constructs active molecular orbitals capable of describing all relevant electronic configurations emerging from a targeted set of atomic valence orbitals (e.g., the metal d orbitals in a coordination complex). This is achieved via a linear transformation of the occupied and unoccupied orbital spaces from an easily obtainable single-reference wave function (such as from a Hartree-Fock or Kohn-Sham calculations) based on projectors to targeted atomic valence orbitals. We discuss the premises, theory, and implementation of the idea, and several of its variations are tested. To investigate the performance and accuracy, we calculate the excitation energies for various transition-metal complexes in typical application scenarios. Additionally, we follow the homolytic bond breaking process of a Fenton reaction along its reaction coordinate. While the described AVAS technique is not a universal solution to the active space problem, its premises are fulfilled in many application scenarios of transition-metal chemistry and bond dissociation processes. In these cases the technique makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.

Original languageEnglish (US)
Pages (from-to)4063-4078
Number of pages16
JournalJournal of Chemical Theory and Computation
Volume13
Issue number9
DOIs
StatePublished - Sep 12 2017

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Coordination Complexes
valence
orbitals
Transition metals
Linear transformations
Excitation energy
Molecular orbitals
Wave functions
Metal complexes
Electronic structure
Metals
transition metals
linear transformations
projectors
emerging
molecular orbitals
wave functions
dissociation
chemistry
electronic structure

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Sayfutyarova, Elvira R. ; Sun, Qiming ; Chan, Garnet Kin Lic ; Knizia, Gerald. / Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals. In: Journal of Chemical Theory and Computation. 2017 ; Vol. 13, No. 9. pp. 4063-4078.
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Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals. / Sayfutyarova, Elvira R.; Sun, Qiming; Chan, Garnet Kin Lic; Knizia, Gerald.

In: Journal of Chemical Theory and Computation, Vol. 13, No. 9, 12.09.2017, p. 4063-4078.

Research output: Contribution to journalArticle

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