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Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals

Publication ,  Journal Article
Janowski, T
Published in: Journal of Chemical Theory and Computation
August 12, 2014

A direct relationship between the Intrinsic Atomic Orbitals (IAO) method (Knizia, G. J. Chem. Theory Comp. 2013, 9, 4834-4843) and earlier work on the same topic, quasiatomic minimal basis set orbitals (QUAMBO) (Lu, W. C.; Wang, C. Z.; Schmidt, M. W.; Bytautas, L.; Ho, K. M.; Ruedenberg J. Chem. Phys. 2004, 2629) and later modifications (quasiatomic orbitals, QUAO) is investigated. It will be demonstrated mathematically that IAOs are almost identical to the original formulation of QUAMBOs and span the same space as a later QUAO modification. The construction of QUAOs involves minimization of a functional that requires matrix diagonalization, or singular matrix decomposition, while the IAO method provides a direct solution by projections. As a byproduct of this proof, it will be shown that (a) under mild conditions a simpler projection yields identical IAOs and (b) an alternative proof is obtained that IAOs span the full space of molecular orbitals if they are linearly independent. Utilization of QUAMBOs as the defining basis set results in rock-solid numerical stability of Pipek-Mezey localization and Mulliken or Löwdin population analysis in very large systems. The charges do not depend on the basis set used, as already shown by Knizia for smaller systems. In this paper, more difficult cases of large semiperiodic systems with strong linear dependency are tested, and it is shown that QUAMBOs perform extremely well. © 2014 American Chemical Society.

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Published In

Journal of Chemical Theory and Computation

DOI

EISSN

1549-9626

ISSN

1549-9618

Publication Date

August 12, 2014

Volume

10

Issue

8

Start / End Page

3085 / 3091

Related Subject Headings

  • Chemical Physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0803 Computer Software
  • 0601 Biochemistry and Cell Biology
  • 0307 Theoretical and Computational Chemistry
 

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Janowski, T. (2014). Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals. Journal of Chemical Theory and Computation, 10(8), 3085–3091. https://doi.org/10.1021/ct500245f
Janowski, T. “Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals.” Journal of Chemical Theory and Computation 10, no. 8 (August 12, 2014): 3085–91. https://doi.org/10.1021/ct500245f.
Janowski T. Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals. Journal of Chemical Theory and Computation. 2014 Aug 12;10(8):3085–91.
Janowski, T. “Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals.” Journal of Chemical Theory and Computation, vol. 10, no. 8, Aug. 2014, pp. 3085–91. Scopus, doi:10.1021/ct500245f.
Janowski T. Near equivalence of intrinsic atomic orbitals and quasiatomic orbitals. Journal of Chemical Theory and Computation. 2014 Aug 12;10(8):3085–3091.
Journal cover image

Published In

Journal of Chemical Theory and Computation

DOI

EISSN

1549-9626

ISSN

1549-9618

Publication Date

August 12, 2014

Volume

10

Issue

8

Start / End Page

3085 / 3091

Related Subject Headings

  • Chemical Physics
  • 3407 Theoretical and computational chemistry
  • 3406 Physical chemistry
  • 0803 Computer Software
  • 0601 Biochemistry and Cell Biology
  • 0307 Theoretical and Computational Chemistry