ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Ground-state rotational spectra of the seven isotopomers H2O(centered ellipsis)35Cl2, H2O(centered ellipsis)37Cl35Cl, H2O(centered ellipsis)35Cl37Cl, D2O(centered ellipsis)35Cl2, D2O(centered ellipsis)37Cl35Cl, HDO(centered ellipsis)35Cl2, and HDO(centered ellipsis)37Cl35Cl of the complex formed between water and dichlorine were observed by pulsed-jet, Fourier-transform microwave spectroscopy. Rotational constants B0 and C0, centrifugal distortion constants ΔJ and ΔJK, and Cl nuclear quadrupole coupling constants χaa(Clx) and {χbb(Clx)−χcc(Clx)}, where x=i (inner) or o (outer), were obtained via spectral analyses. The spectroscopic constants were interpreted, on the basis of models for the complex, to give the geometry, the binding strength, and the extent of inter- and intramolecular electron transfer on complex formation. The zero-point geometry is defined in terms of the effective values r(O(centered ellipsis)Cli)=2.8479(3) Å and φ=43.4(3)°, where φ is the angle made by the bisector of the HÔH angle with the O(centered ellipsis)Cl internuclear line. The intermolecular stretching force constant kσ=8.0(1) N m−1. Fractions δi=0.005(5) and δp=0.034(3) of an electron were estimated to be transferred from O to Cl and from Cli to Clo, respectively. The geometrical conclusions are supported by ab initio calculations at the aug-cc-pVDZ/MP2 level of theory, with good agreement for φ and r(O(centered ellipsis)Cli). A comparison of the properties of H2O(centered ellipsis)Cl2 with those of H2O(centered ellipsis)HCl provides evidence in support of a recent proposal of a halogen bond B(centered ellipsis)XY that is the analog of the hydrogen bond B(centered ellipsis)HX, where X and Y are halogen atoms. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1354178
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