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Journal of Chemical Physics / Volume 126 / Issue 8 / ARTICLES / Biological Molecules, Biopolymers, and Biological Systems

J. Chem. Phys. 126, 085101 (2007); http://dx.doi.org/10.1063/1.2436890 (7 pages)

Coupled-cluster and explicitly correlated perturbation-theory calculations of the uracil anion

Rafał A. Bachorz1, Wim Klopper1, and Maciej Gutowski2

1Center for Functional Nanostructures (CFN), Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany and Lehrstuhl für Theoretische Chemie, Institut für Physikalische Chemie, Universität Karlsruhe (TH), D-76128 Karlsruhe, Germany
2Department of Chemistry, School of Engineering and Physical Sciences, Heriot-Watt University, William H Perkin Building, EH14 4AS Edinburgh, United Kingdom and Department of Chemistry, University of Gdańsk, 80-952 Gdańsk, Poland

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(Received 22 November 2006; accepted 3 January 2007; published online 27 February 2007)

A valence-type anion of the canonical tautomer of uracil has been characterized using explicitly correlated second-order Møller-Plesset perturbation theory (RI-MP2-R12) in conjunction with conventional coupled-cluster theory with single, double, and perturbative triple excitations. At this level of electron-correlation treatment and after inclusion of a zero-point vibrational energy correction, determined in the harmonic approximation at the RI-MP2 level of theory, the valence anion is adiabatically stable with respect to the neutral molecule by 40 meV. The anion is characterized by a vertical detachment energy of 0.60 eV. To obtain accurate estimates of the vertical and adiabatic electron binding energies, a scheme was applied in which electronic energy contributions from various levels of theory were added, each of them extrapolated to the corresponding basis-set limit. The MP2 basis-set limits were also evaluated using an explicitly correlated approach, and the results of these calculations are in agreement with the extrapolated values. A remarkable feature of the valence anionic state is that the adiabatic electron binding energy is positive but smaller than the adiabatic electron binding energy of the dipole-bound state.

© 2007 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. METHODS
    1. The RI-MP2-R12 method for open-shell systems
    2. Geometries and harmonic vibrational frequencies
    3. Extrapolated Hartree-Fock energies
    4. Extrapolated correlation energies
    5. Best estimates of AEA and VDE
  3. RESULTS
  4. SUMMARY

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KEYWORDS and PACS

Keywords

organic compounds, perturbation theory, vibrational states, binding energy, electron correlations, molecular electronic states

PACS

  • 31.15.-p

    Calculations and mathematical techniques in atomic and molecular physics

  • 33.15.Ry

    Ionization potentials, electron affinities, molecular core binding energy

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2436890

PUBLICATION DATA

ISSN

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

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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