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Title: CCSD(T) calculations of stabilities and properties of confined systems

We analyze energies, electron affinities and polarizabilities of small anions exposed to an external confinement. The second electron in free O{sup 2−} and S{sup 2−} anions is unbound. We investigate the stabilizing effect of the spherical harmonic-oscillator confining potential ω. on these anions employing the Hartree-Fock stability analysis as introduced by Čížek and Paldus. With increasing strength of the external harmonic-oscillator confinement potential ω the broken symmetry (BS) solutions are systematically eliminated. For ω larger than 0.1 all BS solutions for O{sup 2−} disappear. For ω larger than 0.13 the CCSD(T) energy of O{sup 2−} becomes more negative than the energy of the singly charged O{sup −} anion. We relate the harmonic-oscillator confining potential to a crystalline environment in which the O{sup 2−} and S{sup 2−} anions are stable. We also present a model allowing calculations of the in-crystal polarizabilities of anions. The model is based on CCSD(T) calculations of static polarizabilities of selected anions exposed to the spherical harmonic-oscillator confining potential ω This artificial confinement potential ω is then related to the ionic radii of the cation in representative crystal lattices. We investigate the polarizability of O{sup 2−} and S{sup 2−} anions in MgO, MgS, CaO, CaS, SrO, SrS,more » BaO and BaS crystals. We compare our results with alternative models for in-crystal polarizabilities. External confinement also stabilizes the uracil anion U{sup −}, as is shown by calculations with a stepwise micro-hydration of U{sup −}. Upon hydration is the CCSD(T) adiabatic electron affinity (AEA) of uracil enhanced by about 250 up to 570 meV in comparison with AEA of the isolated molecule, depending on the geometry of the hydrated uracil anion complex. We tried to find an analogy of the stabilization effect of the external confinement on the otherwise unstable anions. In uracil and its anion is the external confinement represented by the polarized continuum solvation model with dielectric constant as a variational parameter. The physical behavior of ions exposed to an artificial external, spherical harmonic-oscillator confining potential ω, the environment represented by a crystal structure and the confinement represented by the solvent, all have considerable stabilizing effect on the otherwise unstable free anion.« less
Authors:
;  [1] ; ;  [2] ;  [3]
  1. Slovak University of Technology in Bratislava, Faculty of Materials Science and Technology in Trnava, Institute of Materials Science, Bottova 25, SK-917 24 Trnava (Slovakia)
  2. Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina, SK-842 15 Bratislava (Slovakia)
  3. Department of Applied Mathematics, University of Waterloo, N2L 3G1, Ontario (Canada)
Publication Date:
OSTI Identifier:
22390911
Resource Type:
Journal Article
Resource Relation:
Journal Name: AIP Conference Proceedings; Journal Volume: 1642; Journal Issue: 1; Conference: ICCMSE-2010: International Conference of Computational Methods in Sciences and Engineering 2010, Kos (Greece), 3-8 Oct 2010; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ANIONS; BARIUM OXIDES; BARIUM SULFIDES; CALCIUM SULFIDES; CATIONS; COMPARATIVE EVALUATIONS; CRYSTAL STRUCTURE; CRYSTALS; ELECTRONS; HARMONIC OSCILLATORS; HARTREE-FOCK METHOD; HYDRATION; MAGNESIUM SULFIDES; MOLECULES; PERMITTIVITY; POLARIZABILITY; POTENTIALS; STRONTIUM OXIDES; SYMMETRY BREAKING; URACILS