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Highly multireferenced arynes studied with large active spaces using two-electron reduced density matrices

J. Chem. Phys. 130, 184101 (2009); doi:10.1063/1.3127402

Published 8 May 2009

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Loren Greenman and David A. Mazziotti
Department of Chemistry and The James Franck Institute, The University of Chicago, Chicago, Illinois 60637, USA
Using the active-space two-electron reduced density matrix (2-RDM) method, which scales polynomially with the size of the active space [G. Gidofalvi and D. A. Mazziotti, J. Chem. Phys. 129, 134108 (2008)], we were able to use active spaces as large as 24 electrons in 24 orbitals in computing the ground-state energies and properties of highly multireferenced arynes. Because the conventional complete-active-space self-consistent-field (CASSCF) method scales exponentially with the size of the active space, its application to arynes was mainly limited to active spaces of 12 electrons in 12 orbitals. For these smaller active spaces the active-space 2-RDM method accurately reproduces the results of CASSCF. However, we show that the larger active spaces are necessary for describing changes in energies and properties with aryne chain length such as the emergence of polyradical character. Furthermore, the addition of further electron correlation by multireference perturbation theory is demonstrated to be inadequate for removing the limitations of the smaller active spaces. ©2009 American Institute of Physics
History: Received 1 February 2009; accepted 8 April 2009; published 8 May 2009
Permalink: http://link.aip.org/link/?JCPSA6/130/184101/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.20.Fz
    Macromolecular constitution (chains and sequences)
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • 31.15.xr
    Self-consistent-field methods in atomic and molecular physics
  • 31.15.vq
    Electron correlation calculations for polyatomic molecules
  • 31.15.xp
    Perturbation theory in atomic and molecular physics
  • 36.20.Hb
    Macromolecular configuration (bonds, dimensions)
  • YEAR: 2009

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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