Distortion of ethyne on formation of a π complex with silver chloride: C 2H 2Ag-Cl characterised by rotational spectroscopy and ab initio calculations

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

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Abstract

C 2H 2Ag-Cl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. Reaction of laser-ablated silver metal with CCl 4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues 12C 2H 2 107Ag 35Cl, 12C 2H 2 109Ag 35Cl, 12C 2H 2 107Ag 37Cl, 12C 2H 2 109Ag 37Cl, 13C 2H 2 107Ag 35Cl, and 13C 2H 2 109Ag 35Cl were analysed to yield rotational constants A 0, B 0, and C 0, centrifugal distortion constants Δ J, Δ JK, and δ J, and Cl nuclear quadrupole coupling constants χ aa(Cl) and χ bb(Cl) -χ cc(Cl). A less complete analysis was possible for 12C 2D 2 107Ag 35Cl and 12C 2D 2 109Ag 35Cl. Observed principal moments of inertia were interpreted in terms of a planar, T-shaped geometry of C 2v symmetry in which the AgCl molecule lies along a C 2 axis of ethyne and the Ag atom forms a bond to the midpoint () of the ethyne π bond. r 0 and rm(1) geometries and an almost complete r s-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the CC bond and movement of the two H atoms away from the CC internuclear line and the Ag atom. The rm(1) bond lengths and angles are as follows: r(Ag) 2.1800(3) Å, r(C-C) 1.2220(20) Å, r(Ag-Cl) 2.2658(3) Å and the angle H-C has the value 187.79(1)°. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12)cc-pVTZ yield a r e geometry in excellent agreement with the experimental rm(1)version, including the ethyne angular distortion.

Original languageEnglish
Article number174302
JournalJournal of Chemical Physics
Volume137
Issue number17
DOIs
Publication statusPublished - Nov 7 2012
Externally publishedYes

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silver chlorides
Acetylene
Spectroscopy
rotational spectra
geometry
spectroscopy
Geometry
atoms
Atoms
moments of inertia
Microwave spectroscopy
molecules
Molecules
quadrupoles
silver
Bond length
vapor phases
Silver
microwaves
Ground state

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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Distortion of ethyne on formation of a π complex with silver chloride : C 2H 2Ag-Cl characterised by rotational spectroscopy and ab initio calculations. / Stephens, Susanna L.; Mizukami, Wataru; Tew, David P.; Walker, Nicholas R.; Legon, Anthony C.

In: Journal of Chemical Physics, Vol. 137, No. 17, 174302, 07.11.2012.

Research output: Contribution to journalArticle

Stephens, Susanna L. ; Mizukami, Wataru ; Tew, David P. ; Walker, Nicholas R. ; Legon, Anthony C. / Distortion of ethyne on formation of a π complex with silver chloride : C 2H 2Ag-Cl characterised by rotational spectroscopy and ab initio calculations. In: Journal of Chemical Physics. 2012 ; Vol. 137, No. 17.
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abstract = "C 2H 2Ag-Cl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. Reaction of laser-ablated silver metal with CCl 4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues 12C 2H 2 107Ag 35Cl, 12C 2H 2 109Ag 35Cl, 12C 2H 2 107Ag 37Cl, 12C 2H 2 109Ag 37Cl, 13C 2H 2 107Ag 35Cl, and 13C 2H 2 109Ag 35Cl were analysed to yield rotational constants A 0, B 0, and C 0, centrifugal distortion constants Δ J, Δ JK, and δ J, and Cl nuclear quadrupole coupling constants χ aa(Cl) and χ bb(Cl) -χ cc(Cl). A less complete analysis was possible for 12C 2D 2 107Ag 35Cl and 12C 2D 2 109Ag 35Cl. Observed principal moments of inertia were interpreted in terms of a planar, T-shaped geometry of C 2v symmetry in which the AgCl molecule lies along a C 2 axis of ethyne and the Ag atom forms a bond to the midpoint () of the ethyne π bond. r 0 and rm(1) geometries and an almost complete r s-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the CC bond and movement of the two H atoms away from the CC internuclear line and the Ag atom. The rm(1) bond lengths and angles are as follows: r(Ag) 2.1800(3) {\AA}, r(C-C) 1.2220(20) {\AA}, r(Ag-Cl) 2.2658(3) {\AA} and the angle H-C has the value 187.79(1)°. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12)cc-pVTZ yield a r e geometry in excellent agreement with the experimental rm(1)version, including the ethyne angular distortion.",
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AB - C 2H 2Ag-Cl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. Reaction of laser-ablated silver metal with CCl 4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues 12C 2H 2 107Ag 35Cl, 12C 2H 2 109Ag 35Cl, 12C 2H 2 107Ag 37Cl, 12C 2H 2 109Ag 37Cl, 13C 2H 2 107Ag 35Cl, and 13C 2H 2 109Ag 35Cl were analysed to yield rotational constants A 0, B 0, and C 0, centrifugal distortion constants Δ J, Δ JK, and δ J, and Cl nuclear quadrupole coupling constants χ aa(Cl) and χ bb(Cl) -χ cc(Cl). A less complete analysis was possible for 12C 2D 2 107Ag 35Cl and 12C 2D 2 109Ag 35Cl. Observed principal moments of inertia were interpreted in terms of a planar, T-shaped geometry of C 2v symmetry in which the AgCl molecule lies along a C 2 axis of ethyne and the Ag atom forms a bond to the midpoint () of the ethyne π bond. r 0 and rm(1) geometries and an almost complete r s-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the CC bond and movement of the two H atoms away from the CC internuclear line and the Ag atom. The rm(1) bond lengths and angles are as follows: r(Ag) 2.1800(3) Å, r(C-C) 1.2220(20) Å, r(Ag-Cl) 2.2658(3) Å and the angle H-C has the value 187.79(1)°. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12)cc-pVTZ yield a r e geometry in excellent agreement with the experimental rm(1)version, including the ethyne angular distortion.

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