High level ab initio calculations on ClFn (n = 1–6): Recoupled pair bonding involving a closed-shell central ion

Lina Chen, David E. Woon, Thom H. Dunning

Research output: Contribution to journalArticlepeer-review


In this paper we complete our studies of the bonding in the ClFn +,0,− series, characterizing the structures and energetics of the ground and low-lying excited states of ClFn (n = 1–6) via coupled cluster calculations with large correlation consistent basis sets and interpreting the results of the calculations using concepts from generalized valence bond (GVB) theory. The chlorine anion is isoelectronic with the argon atom, possessing three 3p lone pairs. However, the electrons in Cl are much less tightly bound than those of Ar, and it is thus possible for the fluorine atom to form recoupled pair bonds and recoupled pair bond dyads with the chlorine anion even if this is not possible with the argon atom. The calculated dissociation energies, D0(Fn −1Cl[sbnd]F), for the anions are 28.9, 72.3, 12.5, 59.9, 4.5, and 38.8 kcal/mol for n = 1–6, and the adiabatic electron affinities, EA0(ClFn), are 2.25, 4.78, 3.29, 5.47, 3.80, and 5.43 eV, respectively [CCSD(T)/RCCSD(T)/AVQ+Z]. Unlike the cation series, the ClFn anions have competing dissociation channels, ClFn  → ClFn −1 + F and ClFn  → ClFn −1  + F, because of the similar electron affinities of the fluorine atom and some of the ClFn −1 species. The ClF2 and ClF4 anions dissociate to F and (ClF, ClF3), while the remaining members of the family dissociate to F and ClFn −1 . However, the electronic structure of the ClF2 species at its equilibrium geometry is consistent with the addition of a fluorine atom to ClF. In addition to the ground states of ClFn , three previously unknown excited states were found for ClF2 , ClF3 , and ClF4 with excitation energies of ΔE0 = 2.24, 2.02 and 2.11 eV, respectively. In contrast to the ground states, which possess the maximum number of recoupled pair bond dyads, the excited state species have one fewer dyad and two additional recoupled pair bonds.

Original languageEnglish (US)
Pages (from-to)73-85
Number of pages13
JournalComputational and Theoretical Chemistry
StatePublished - Sep 15 2017


  • Bond energies
  • Chlorine fluoride anions
  • Coupled cluster methods
  • Electron affinities
  • Generalized valence bond theory
  • Hypervalent molecules
  • Recoupled pair bonding

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry


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