Projects per year

### Abstract

C2H2 center dot center dot center dot 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 CCl4 gave AgCl which then reacted with ethyne to give the complex. Ground-state rotational spectra of the six isotopologues (C2H2)-C-12 center dot center dot center dot(AgCl)-Ag-107-Cl-35, (C2H2)-C-12 center dot center dot center dot(AgCl)-Ag-109-Cl-35, (C2H2)-C-12 center dot center dot center dot(AgCl)-Ag-107-Cl-37, (C2H2)-C-12 center dot center dot center dot(AgCl)-Ag-109-Cl-37, (C2H2)-C-13 center dot center dot center dot 107Ag(35)Cl, and (C2H2)-C-13 center dot center dot center dot(AgCl)-Ag-109-Cl-35 were analysed to yield rotational constants A(0), B-0, and C-0, centrifugal distortion constants Delta J, Delta JK, and delta J, and Cl nuclear quadrupole coupling constants chi aa(Cl) and chi bb(Cl) -chi cc(Cl). A less complete analysis was possible for (C2D2)-C-12 center dot center dot center dot(AgCl)-Ag-107-Cl-35 and (C2D2)-C-12 center dot center dot center dot(AgCl)-Ag-109-Cl-35. 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 pi bond. r(0) and r(m)((1)) geometries and an almost complete rs-geometry were established. The ethyne molecule distorts on complex formation by lengthening of the C equivalent to C bond and movement of the two H atoms away from the C equivalent to C internuclear line and the Ag atom. The r(m)((1)) bond lengths and angles are as follows: r(*center dot Ag) = 2.1800(3) A degrees, r(C-C) = 1.2220(20) A degrees, r(Ag-Cl) = 2.2658(3) A degrees and the angle H-C equivalent to* has the value 187.79(1)degrees. Ab initio calculations at the coupled-cluster singles and doubles level of theory with a perturbative treatment of triples (F12*)/cc-pVTZ yield a re geometry in excellent agreement with the experimental r(m)((1))version, including the ethyne angular distortion. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4761895]

Original language | English |
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Article number | 174302 |

Number of pages | 13 |

Journal | Journal of Chemical Physics |

Volume | 137 |

Issue number | 17 |

DOIs | |

Publication status | Published - 7 Nov 2012 |

### Keywords

- ab initio calculations
- association
- bond angles
- bond lengths
- coupled cluster calculations
- Fourier transform spectra
- ground states
- microwave spectra
- molecular configurations
- organometallic compounds
- quadrupole coupling
- rotational states
- CORRELATED MOLECULAR CALCULATIONS
- GAUSSIAN-BASIS SETS
- TRANSFORM MICROWAVE SPECTROSCOPY
- HYDROGEN-BONDED DIMERS
- ELECTRIC-DIPOLE MOMENT
- CENTER-DOT-HCL
- GAS-PHASE
- HYPERFINE CONSTANTS
- PHOTODISSOCIATION SPECTROSCOPY
- ATOMS ALUMINUM

## Projects

- 1 Finished

## CHARACTERISATION OF METAL NANOCLUSTERS AND CATALYTIC MECHANISMS BY MICROWAVE SPECTROSCOPY

Walker, N. R.

1/09/09 → 1/03/13

Project: Research

## Cite this

*Journal of Chemical Physics*,

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