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Relative energies and geometries of the cis- and trans-HO3 radicals from the parametric 2-electron density matrix method.
Journal of Physical Chemistry A (2013)
  • Erik P. Hoy, Rowan University
  • Christine A. Schwerdtfeger
  • David A. Mazziotti
Abstract
The parametric 2-electron reduced density matrix (2-RDM) method employing the M functional [Mazziotti, D. A. Phys. Rev. Lett. 2008, 101, 253002], also known as the 2-RDM(M) method, improves on the accuracy of coupled electron-pair theories including coupled cluster with single-double excitations at the computational cost of configuration interaction with single-double excitations. The cis- and trans-HO(3) isomers along with their isomerization transition state were examined using the recent extension of 2-RDM(M) to nonsinglet open-shell states [Schwerdtfeger, C. A.; Mazziotti, D. A. J. Chem. Phys. 2012, 137, 034107] and several coupled cluster methods. We report the calculated energies, geometries, natural-orbital occupation numbers, and reaction barriers for the HO(3) isomers. We find that the 2-RDM(M) method predicts that the trans isomer of HO(3) is lower in energy than the cis isomer by 1.71 kcal/mol in the correlation-consistent polarized valence quadruple-ζ (cc-pVQZ) basis set and 1.84 kcal/mol in the augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set. Results include the harmonic zero-point vibrational energies calculated in the correlation-consistent polarized valence double-ζ basis set. On the basis of the results of a geometry optimization in the augmented correlation consistent polarized valence triple-ζ basis set, the parametric 2-RDM(M) method predicts a central oxygen-oxygen bond of 1.6187 Å. We compare these energies and geometries to those predicted by three single-reference coupled cluster methods and experimental results and find that the inclusion of multireference correlation is important to describe properly the relative energies of the cis- and trans-HO(3) isomers and improve agreement with experimental geometries.
Publication Date
February 28, 2013
DOI
10.1021/jp3105562
Citation Information
Erik P. Hoy, Christine A. Schwerdtfeger and David A. Mazziotti. "Relative energies and geometries of the cis- and trans-HO3 radicals from the parametric 2-electron density matrix method." Journal of Physical Chemistry A Vol. 117 Iss. 8 (2013) p. 1817 - 1825
Available at: http://works.bepress.com/erik-hoy/5/