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

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

Research output: Contribution to journalArticle

4 Citations (Scopus)

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

Fingerprint

Anions
Theoretical Models
detachment
Electrons
dipoles
anions
Hydrofluoric Acid
electrons
Geometry
hydrofluoric acid
geometry
Hydrogen
Polymers
electron scattering
energy
polymers
hydrogen
configurations

Keywords

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

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Ab initio theoretical study of dipole-bound anions of molecular complexes (HF)(n)/-, n = 5-9. / Ramaekers, R.; Smith, D. M A; Smets, J.; Adamowicz, Ludwik.

In: Journal of Molecular Structure, Vol. 513, No. 1-3, 07.12.1999, p. 169-176.

Research output: Contribution to journalArticle

@article{1ab67499717e47589a566535478e38d1,
title = "Ab initio theoretical study of dipole-bound anions of molecular complexes (HF)(n)/-, n = 5-9",
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.",
keywords = "Ab initio calculations, Adiabatically stable systems, Dipole-bound anions, Hydrogen-bonded polymers",
author = "R. Ramaekers and Smith, {D. M A} and J. Smets and Ludwik Adamowicz",
year = "1999",
month = "12",
day = "7",
doi = "10.1016/S0022-2860(99)00117-9",
language = "English (US)",
volume = "513",
pages = "169--176",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",
number = "1-3",

}

TY - JOUR

T1 - Ab initio theoretical study of dipole-bound anions of molecular complexes (HF)(n)/-, n = 5-9

AU - Ramaekers, R.

AU - Smith, D. M A

AU - Smets, J.

AU - Adamowicz, Ludwik

PY - 1999/12/7

Y1 - 1999/12/7

N2 - 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.

AB - 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.

KW - Ab initio calculations

KW - Adiabatically stable systems

KW - Dipole-bound anions

KW - Hydrogen-bonded polymers

UR - http://www.scopus.com/inward/record.url?scp=0033534034&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033534034&partnerID=8YFLogxK

U2 - 10.1016/S0022-2860(99)00117-9

DO - 10.1016/S0022-2860(99)00117-9

M3 - Article

VL - 513

SP - 169

EP - 176

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - 1-3

ER -