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Automated construction of molecular active spaces from atomic valence orbitals

Sayfutyarova, Elvira R. and Sun, Qiming and Chan, Garnet Kin-Lic and Knizia, Gerald (2017) Automated construction of molecular active spaces from atomic valence orbitals. Journal of Chemical Theory and Computation, 13 (9). pp. 4063-4078. ISSN 1549-9618. doi:10.1021/acs.jctc.7b00128.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription Paper
Sayfutyarova, Elvira R.0000-0001-8403-5013
Sun, Qiming0000-0003-0528-6186
Chan, Garnet Kin-Lic0000-0001-8009-6038
Knizia, Gerald0000-0002-7163-4823
Additional Information:© 2017 American Chemical Society. Received: February 7, 2017; Published: July 21, 2017. We acknowledge the US National Science Foundation for funding this research primarily through the award NSF:CHE-1665333. Additional support for software development and to support Q.S. was provided through NSF:CHE-1657286. We acknowledge additional support for G.K.C. from the Simons Foundation through a Simons Investigatorship. The authors declare no competing financial interest.
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Simons FoundationUNSPECIFIED
Issue or Number:9
Record Number:CaltechAUTHORS:20170206-112454455
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Official Citation:Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals Elvira R. Sayfutyarova, Qiming Sun, Garnet Kin-Lic Chan, and Gerald Knizia Journal of Chemical Theory and Computation 2017 13 (9), 4063-4078 DOI: 10.1021/acs.jctc.7b00128
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74079
Deposited By: Donna Wrublewski
Deposited On:06 Feb 2017 20:19
Last Modified:11 Nov 2021 05:24

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