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Abstract
C2H2 center dot center dot center dot AgCl was formed from ethyne and AgCl in the gas phase and its rotational spectrum observed by both the chirpedpulse and FabryPerot cavity versions of Fouriertransform microwave spectroscopy. Reaction of laserablated silver metal with CCl4 gave AgCl which then reacted with ethyne to give the complex. Groundstate rotational spectra of the six isotopologues (C2H2)C12 center dot center dot center dot(AgCl)Ag107Cl35, (C2H2)C12 center dot center dot center dot(AgCl)Ag109Cl35, (C2H2)C12 center dot center dot center dot(AgCl)Ag107Cl37, (C2H2)C12 center dot center dot center dot(AgCl)Ag109Cl37, (C2H2)C13 center dot center dot center dot 107Ag(35)Cl, and (C2H2)C13 center dot center dot center dot(AgCl)Ag109Cl35 were analysed to yield rotational constants A(0), B0, and C0, 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)C12 center dot center dot center dot(AgCl)Ag107Cl35 and (C2D2)C12 center dot center dot center dot(AgCl)Ag109Cl35. Observed principal moments of inertia were interpreted in terms of a planar, Tshaped geometry of C2v symmetry in which the AgCl molecule lies along a C2 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 rsgeometry 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(CC) = 1.2220(20) A degrees, r(AgCl) = 2.2658(3) A degrees and the angle HC equivalent to* has the value 187.79(1)degrees. Ab initio calculations at the coupledcluster singles and doubles level of theory with a perturbative treatment of triples (F12*)/ccpVTZ 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 

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
 GAUSSIANBASIS SETS
 TRANSFORM MICROWAVE SPECTROSCOPY
 HYDROGENBONDED DIMERS
 ELECTRICDIPOLE MOMENT
 CENTERDOTHCL
 GASPHASE
 HYPERFINE CONSTANTS
 PHOTODISSOCIATION SPECTROSCOPY
 ATOMS ALUMINUM
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Dive into the research topics of 'Distortion of ethyne on formation of a pi complex with silver chloride: C2H2 center dot center dot center dot AgCl characterised by rotational spectroscopy and ab initio calculations'. Together they form a unique fingerprint.Projects
 1 Finished

CHARACTERISATION OF METAL NANOCLUSTERS AND CATALYTIC MECHANISMS BY MICROWAVE SPECTROSCOPY
Walker, N. R.
1/09/09 → 1/03/13
Project: Research