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On the rotational energy distributions of reactive, non-polar species in the interstellar medium
Astrophysics and Space Science (2013)
  • Robert J. Glinski, Tennessee Technological University
  • Erik P. Hoy, Rowan University
  • Clark R. Downum, Tennessee Technological University
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
January 1, 2013
DOI
10.1007/s10509-012-1238-8
Citation Information
Robert J. Glinski, Erik P. Hoy and Clark R. Downum. "On the rotational energy distributions of reactive, non-polar species in the interstellar medium" Astrophysics and Space Science Vol. 343 Iss. 1 (2013) p. 319 - 327
Available at: http://works.bepress.com/erik-hoy/6/