## 抄録

The rotational spectra of six isotopologues of a complex of ethyne and silver acetylide, C_{2}H_{2}⋯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% C_{2}H_{2}, 1% SF_{6}, and 98% Ar undergoing supersonic expansion. Rotational, A _{0}, B_{0}, C_{0}, and centrifugal distortion Δ_{J} and Δ_{JK} constants are determined for all isotopologues of C_{2}H_{2}⋯AgCCH studied. The geometry is planar, C_{2v} and T-shaped in which the C_{2}H_{2} sub-unit comprises the bar of the "T" and binds to the metal atom through its π electrons. In the r_{0} geometry, the distance of the Ag atom from the centre of the triple bond in C_{2}H_{2} 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 C_{2}H_{2} sub-unit, are determined to be 1.2200(24) Å and 186.0(5)°, respectively. This distortion of the linear geometry of C _{2}H_{2} involves the hydrogen atoms moving away from the silver atom within the complex. The results thus reveal that the geometry of C_{2}H_{2} changes measurably on coordination to AgCCH. A value of 59(4) N m^{-1} is determined for the intermolecular force constant, k_{Σ}, confirming that the complex is significantly more strongly bound than hydrogen and halogen-bonded analogues. Ab initio calculations of the r_{e} geometry at the CCSD(T)(F12^{*})/ACVTZ level of theory are consistent with the experimental results. The spectra of the ^{107}Ag^{13}C^{13}CH and ^{109}Ag ^{13}C^{13}CH 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 |

巻 | 140 |

号 | 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_{2}H

_{2}⋯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。