### Abstract

C _{2}H _{2}Ag-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 ^{12}C _{2}H _{2} ^{107}Ag ^{35}Cl, ^{12}C _{2}H _{2} ^{109}Ag ^{35}Cl, ^{12}C _{2}H _{2} ^{107}Ag ^{37}Cl, ^{12}C _{2}H _{2} ^{109}Ag ^{37}Cl, ^{13}C _{2}H _{2} ^{107}Ag ^{35}Cl, and ^{13}C _{2}H _{2} ^{109}Ag ^{35}Cl 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 ^{12}C _{2}D _{2} ^{107}Ag ^{35}Cl and ^{12}C _{2}D _{2} ^{109}Ag ^{35}Cl. 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 language | English |
---|---|

Article number | 174302 |

Journal | Journal of Chemical Physics |

Volume | 137 |

Issue number | 17 |

DOIs | |

Publication status | Published - Nov 7 2012 |

Externally published | Yes |

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### All Science Journal Classification (ASJC) codes

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

### Cite this

_{2}H

_{2}Ag-Cl characterised by rotational spectroscopy and ab initio calculations.

*Journal of Chemical Physics*,

*137*(17), [174302]. https://doi.org/10.1063/1.4761895

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

Research output: Contribution to journal › Article

_{2}H

_{2}Ag-Cl characterised by rotational spectroscopy and ab initio calculations',

*Journal of Chemical Physics*, vol. 137, no. 17, 174302. https://doi.org/10.1063/1.4761895

_{2}H

_{2}Ag-Cl characterised by rotational spectroscopy and ab initio calculations. Journal of Chemical Physics. 2012 Nov 7;137(17). 174302. https://doi.org/10.1063/1.4761895

}

TY - JOUR

T1 - Distortion of ethyne on formation of a π complex with silver chloride

T2 - C 2H 2Ag-Cl characterised by rotational spectroscopy and ab initio calculations

AU - Stephens, Susanna L.

AU - Mizukami, Wataru

AU - Tew, David P.

AU - Walker, Nicholas R.

AU - Legon, Anthony C.

PY - 2012/11/7

Y1 - 2012/11/7

N2 - 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.

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.

UR - http://www.scopus.com/inward/record.url?scp=84868713153&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84868713153&partnerID=8YFLogxK

U2 - 10.1063/1.4761895

DO - 10.1063/1.4761895

M3 - Article

C2 - 23145726

AN - SCOPUS:84868713153

VL - 137

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

M1 - 174302

ER -