Distortion of ethyne on coordination to silver acetylide, C 2H2⋯AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations

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

Research output: Contribution to journalArticle

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Abstract

The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C2H2⋯AgCCH, are measured by both chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. The complex is generated through laser ablation of a silver target in the presence of a gas sample containing 1% C2H2, 1% SF6, and 98% Ar undergoing supersonic expansion. Rotational, A 0, B0, C0, and centrifugal distortion ΔJ and ΔJK constants are determined for all isotopologues of C2H2⋯AgCCH studied. The geometry is planar, C2v and T-shaped in which the C2H2 sub-unit comprises the bar of the "T" and binds to the metal atom through its π electrons. In the r0 geometry, the distance of the Ag atom from the centre of the triple bond in C2H2 is 2.2104(10) Å. The r(HC≡CH) parameter representing the bond distance separating the two carbon atoms and the angle, (CCH), each defined within the C2H2 sub-unit, are determined to be 1.2200(24) Å and 186.0(5)°, respectively. This distortion of the linear geometry of C 2H2 involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C2H2 changes measurably on coordination to AgCCH. A value of 59(4) N m-1 is determined for the intermolecular force constant, kΣ, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the re geometry at the CCSD(T)(F12*)/ACVTZ level of theory are consistent with the experimental results. The spectra of the 107Ag13C13CH and 109Ag 13C13CH isotopologues of free silver acetylide are also measured for the first time allowing the geometry of the AgCCH monomer to be examined in greater detail than previously.

Original languageEnglish
Article number124310
JournalJournal of Chemical Physics
Volume140
Issue number12
DOIs
Publication statusPublished - Mar 28 2014

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Acetylene
Silver
silver
Spectroscopy
broadband
Geometry
Atoms
geometry
spectroscopy
atoms
Hydrogen
Microwave spectroscopy
Halogens
intermolecular forces
rotational spectra
Laser ablation
halogens
laser ablation
hydrogen atoms
Fourier transforms

All Science Journal Classification (ASJC) codes

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

Cite this

Distortion of ethyne on coordination to silver acetylide, C 2H2⋯AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations. / Stephens, Susanna L.; Zaleski, Daniel P.; Mizukami, Wataru; Tew, David P.; Walker, Nicholas R.; Legon, Anthony C.

In: Journal of Chemical Physics, Vol. 140, No. 12, 124310, 28.03.2014.

Research output: Contribution to journalArticle

Stephens, Susanna L. ; Zaleski, Daniel P. ; Mizukami, Wataru ; Tew, David P. ; Walker, Nicholas R. ; Legon, Anthony C. / Distortion of ethyne on coordination to silver acetylide, C 2H2⋯AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations. In: Journal of Chemical Physics. 2014 ; Vol. 140, No. 12.
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abstract = "The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C2H2⋯AgCCH, are measured by both chirped-pulse and Fabry-Perot cavity versions of Fourier-transform microwave spectroscopy. The complex is generated through laser ablation of a silver target in the presence of a gas sample containing 1{\%} C2H2, 1{\%} SF6, and 98{\%} Ar undergoing supersonic expansion. Rotational, A 0, B0, C0, and centrifugal distortion ΔJ and ΔJK constants are determined for all isotopologues of C2H2⋯AgCCH studied. The geometry is planar, C2v and T-shaped in which the C2H2 sub-unit comprises the bar of the {"}T{"} and binds to the metal atom through its π electrons. In the r0 geometry, the distance of the Ag atom from the centre of the triple bond in C2H2 is 2.2104(10) {\AA}. The r(HC≡CH) parameter representing the bond distance separating the two carbon atoms and the angle, (CCH), each defined within the C2H2 sub-unit, are determined to be 1.2200(24) {\AA} and 186.0(5)°, respectively. This distortion of the linear geometry of C 2H2 involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C2H2 changes measurably on coordination to AgCCH. A value of 59(4) N m-1 is determined for the intermolecular force constant, kΣ, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the re geometry at the CCSD(T)(F12*)/ACVTZ level of theory are consistent with the experimental results. The spectra of the 107Ag13C13CH and 109Ag 13C13CH isotopologues of free silver acetylide are also measured for the first time allowing the geometry of the AgCCH monomer to be examined in greater detail than previously.",
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