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 language | English |
|---|---|
| Pages (from-to) | 47-53 |
| Number of pages | 7 |
| Journal | Journal of Molecular Spectroscopy |
| Volume | 280 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - Oct 1 2012 |
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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 journal › Article
}
TY - JOUR
T1 - The halogen bond between ethene and a simple perfluoroiodoalkane
T2 - C 2H 4⋯ICF 3 identified by broadband rotational spectroscopy
AU - Stephens, Susanna L.
AU - Mizukami, Wataru
AU - Tew, David P.
AU - Walker, Nicholas R.
AU - Legon, Anthony C.
PY - 2012/10/1
Y1 - 2012/10/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84867679404&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84867679404&partnerID=8YFLogxK
U2 - 10.1016/j.jms.2012.06.002
DO - 10.1016/j.jms.2012.06.002
M3 - Article
AN - SCOPUS:84867679404
VL - 280
SP - 47
EP - 53
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
SN - 0022-2852
IS - 1
ER -