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

研究成果: ジャーナルへの寄稿学術誌査読

11 被引用数 (Scopus)

抄録

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.

本文言語英語
論文番号124310
ジャーナルJournal of Chemical Physics
140
12
DOI
出版ステータス出版済み - 3月 28 2014
外部発表はい

!!!All Science Journal Classification (ASJC) codes

  • 物理学および天文学(全般)
  • 物理化学および理論化学

フィンガープリント

「Distortion of ethyne on coordination to silver acetylide, C 2H2⋯AgCCH, characterised by broadband rotational spectroscopy and ab initio calculations」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

引用スタイル