Ab initio theoretical study of dipole-bound anions of molecular complexes (HF)(n)/-, n = 5-9

R. Ramaekers, D. M.A. Smith, J. Smets, L. Adamowicz

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

Ab initio calculations have been performed to determine structures and electron detachment energies of the hydrogen fluoride hydrogen-bonded polymers, (HF)(n)/-, n = 5-9. In these systems, the excess electron is bound by virtue of the dipole-electron interaction. It was found that, unlike the neutral complexes which form cyclic structures, the equilibrium geometries of the anions have 'zig-zag' linear shapes. For all the five complexes, the predicted vertical detachment energies are positive (307, 363, 405, 437, and 461 meV for (HF)5/-, (HF)6/-, (HF)7/-, (HF)8/-, and (HF)9/-, respectively). These results were obtained at the Moller-Plesset second-order level of theory at the geometries of the anions calculated at the Hartree- Fock level. The calculations also indicate that up to n = 8, the (HF)(n)/- anions are metastable systems with respect to electron detachment and simultaneous transformation of the cluster to the most stable cyclic configurations. However, calculations predict that starting from (HF)9/- the linear HF cluster anions are adiabatically stable systems.

Original languageEnglish (US)
Pages (from-to)169-176
Number of pages8
JournalJournal of Molecular Structure
Volume513
Issue number1-3
DOIs
StatePublished - Dec 7 1999

Keywords

  • Ab initio calculations
  • Adiabatically stable systems
  • Dipole-bound anions
  • Hydrogen-bonded polymers

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

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