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. https://resolver.caltech.edu/CaltechAUTHORS:20170206-112454455
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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.
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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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Issue or Number: | 9 | ||||||||||
DOI: | 10.1021/acs.jctc.7b00128 | ||||||||||
Record Number: | CaltechAUTHORS:20170206-112454455 | ||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170206-112454455 | ||||||||||
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 | ||||||||||
Collection: | CaltechAUTHORS | ||||||||||
Deposited By: | Donna Wrublewski | ||||||||||
Deposited On: | 06 Feb 2017 20:19 | ||||||||||
Last Modified: | 11 Nov 2021 05:24 |
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