The halogen bond between ethene and a simple perfluoroiodoalkane: C 2H 4⋯ICF 3 identified by broadband rotational spectroscopy

Susanna L. Stephens, Wataru Mizukami, David P. Tew, Nicholas R. Walker, Anthony C. Legon

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

An isolated complex of C 2H 4 and ICF 3 has been generated in the gas phase and studied by chirped-pulse, Fourier transform microwave (CP-FTMW) spectroscopy. Ab initio calculations at the CCSD(T)(F12)/VTZ level support the experimental work and further establish the dissociation energy, D e, and dipole moment, μ, of the complex. Rotational constants, B 0 and C 0, the centrifugal distortion constant, Δ J, nuclear quadrupole coupling constants, χ aa (I) and (χ bb(I)-χ cc(I)) and the nuclear spin-rotation coupling constant C bb(I) of the complex are determined from the experimental data. The iodine atom interacts with π-electrons on C 2H 4 resulting in the formation of a linear (∠(CI⋯)) halogen bond (where indicates the centre of the CC bond) and a complex of C s symmetry. The measured rotational constants allow the length of the halogen bond to be determined as 3.434(2) Å in the r 0 geometry. The complex is formally an asymmetric top but with a very low barrier to internal rotation of C 2H 4 about the C 3 axis defined by the CF 3I sub-unit. Adopting an approach also used in a recent study of H 2O⋯ICF 3, other transitions are assigned using the Hamiltonian of a symmetric top molecule.

Original languageEnglish
Pages (from-to)47-53
Number of pages7
JournalJournal of Molecular Spectroscopy
Volume280
Issue number1
DOIs
Publication statusPublished - Oct 1 2012

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Halogens
halogens
Microwave spectroscopy
Spectroscopy
broadband
Hamiltonians
Dipole moment
Iodine
spectroscopy
Fourier transforms
Gases
Atoms
Molecules
Geometry
Electrons
nuclear spin
iodine
dipole moments
quadrupoles
ethylene

All Science Journal Classification (ASJC) codes

  • Atomic and Molecular Physics, and Optics
  • Spectroscopy
  • Physical and Theoretical Chemistry

Cite this

The halogen bond between ethene and a simple perfluoroiodoalkane : C 2H 4⋯ICF 3 identified by broadband rotational spectroscopy. / Stephens, Susanna L.; Mizukami, Wataru; Tew, David P.; Walker, Nicholas R.; Legon, Anthony C.

In: Journal of Molecular Spectroscopy, Vol. 280, No. 1, 01.10.2012, p. 47-53.

Research output: Contribution to journalArticle

Stephens, Susanna L. ; Mizukami, Wataru ; Tew, David P. ; Walker, Nicholas R. ; Legon, Anthony C. / The halogen bond between ethene and a simple perfluoroiodoalkane : C 2H 4⋯ICF 3 identified by broadband rotational spectroscopy. In: Journal of Molecular Spectroscopy. 2012 ; Vol. 280, No. 1. pp. 47-53.
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