Molecular geometry of OC⋅⋅⋅AgI determined by broadband rotational spectroscopy and ab initio calculations

Abstract

Pure rotational spectra of the ground vibrational states of six isotopologues of OC···AgI have been measured by chirped-pulse Fourier transform microwave spectroscopy. The spectra are assigned to determine the rotational constant, B(0), centrifugal distortion constant, D(J), and nuclear quadrupole coupling constant of the iodine atom, χ(aa)(I). The complex is linear. Isotopic substitutions at the silver, carbon, and oxygen atoms allow bond lengths to be established by the r(0), r(s), and r(m)((1)) methods of structure determination. The length of the C-O bond, r(CO), in the r(0) geometry for OC···AgI is 0.008 Å shorter than that found in the free CO molecule. The length of the Ag-I bond, r(AgI), is 0.013 Å shorter than in free AgI. χ(aa)(I) is determined to be -769.84(22) MHz for OC···(107)AgI implying an ionic character of 0.66 for the metal halide bond. Attachment of carbon monoxide to the isolated AgI molecule results in an increase of the ionic character of AgI of 0.12. The molecular structure and spectroscopic parameters determined from the experimental data are presented alongside the results of calculations at the explicitly correlated coupled-cluster singles, doubles and perturbative triples level. Vibrational frequencies, the electric dipole moment, the nuclear quadrupole coupling constant, and the dissociation energy of the molecule have been calculated.

Gas phase complexes of H3N⋯CuF and H3N⋯CuI studied by rotational spectroscopy and ab initio calculations: the effect of X (X = F, Cl, Br, I) in OC⋯CuX and H3N⋯CuX

“…Detailed descriptions of the spectrometer and laser ablation source are provided in ref. 25 and 26. A gas sample containing B4.0% NH 3 and B1.5% SF 6 (when generating H 3 NÁ Á ÁCuF) or CF 3 I (when generating H 3 NÁ Á ÁCuI) is diluted in argon and prepared at a total pressure of 6 bar.…”

Molecular geometries and other properties of H2O⋯AgI and H3N⋯AgI as characterised by rotational spectroscopy and ab initio calculations

“…Microwave spectroscopy has recently been applied to explore the molecular structures of complexes in which a Lewis base is attached to either CuX, AgX, or AuX (where X is a halogen atom) to form L· · · MX, [1][2][3][4][5][6][7][8][9][10][11] where, for example, L = H 2 O, 1,10 H 2 S, 3-5 NH 3 , 12 C 2 H 2 , 6,8,11 or CO. 13,14 The same technique has also been applied to study complexes that are similar in composition and structure but distinct in that L is not a typical Lewis base. For example, H 2 · · · MX, 15,16 Ar· · · MX, [17][18][19] Kr· · · MX, 18,20 and Xe· · · MX 21 have each been characterised.…”

Conformational isomers oftrans-urocanic acid observed by rotational spectroscopy

“…A detailed description of the laser ablation source and chirpedpulse Fourier transform microwave (CP-FTMW) spectrometer used for the experiments has been published previously. [15][16][17][18] Molecules within the expanding gas sample are polarised by a chirped microwave pulse of 1 μs in duration. The 2.0 -8.0 and 7.0 -18.5 GHz bands are probed during distinct experiments, each using a pulse that sweeps across the appropriate frequency band.…”