title: CMM-RS potential for characterization of the properties of the halogen-bonded OC-Cl2 complex, and a comparison with hydrogen-bonded OC-HCl.
abstract: Transitions associated with the vibrations ν₁, ν₁ + ν(b)¹, ν₁ + ν₅¹, and ν₁ + ν₅¹ - ν₅¹ of the complex OC···Cl₂ have been rovibrationally analyzed for several isotopologues involving isotopic substitutions in Cl₂. Spectra were recorded using a recently constructed near-infrared (4.34 to 4.56 μm), quantum-cascade laser spectrometer with cw supersonic slit jet expansion. Spectral analysis allowed precise determination of the ν₅¹ intermolecular vibration of OC-³⁵Cl₂ to be 25.977637(80) cm⁻¹. These results were incorporated with other previously determined data into a spectroscopic database for generation of a five-dimensional morphed potential energy surface. This compound-model morphed potential with radial shifting (CMM-RS) was then used to make more accurate predictions of properties of the OC-³⁵Cl₂ complex including D(e) = 544(5) cm⁻¹, D₀ = 397(5) cm⁻¹, ν₃ = 56.43(4) cm⁻¹, and ν(b)¹ = 85.43(4) cm⁻¹. The CMM-RS potential determined for OC-Cl₂ was also used to compare quantitatively many of the inherent properties of this non-covalent halogen bonded complex with those of the closely related hydrogen-bonded complex OC-HCl, which has a similar dissociation energy D₀. We found that in the ground state, the CO bending amplitude is larger in OC-Cl₂ than in OC-HCl.
authors.affiliation: Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, USA.
authors.forename: Sean D
authors.initials: SD
authors.lastname: Springer
authors.forename: Luis A
authors.initials: LA
authors.lastname: Rivera-Rivera
authors.forename: Blake A
authors.initials: BA
authors.lastname: McElmurry
authors.forename: Zhongcheng
authors.initials: Z
authors.lastname: Wang
authors.forename: Igor I
authors.initials: II
authors.lastname: Leonov
authors.forename: Robert R
authors.initials: RR
authors.lastname: Lucchese
authors.forename: Anthony C
authors.initials: AC
authors.lastname: Legon
authors.forename: John W
authors.initials: JW
authors.lastname: Bevan
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D006851:Hydrochloric Acid / Q000737:chemistry*; D006860:Hydrogen Bonding; D010100:Oxygen / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D002712:Chlorides; D002244:Carbon; D006851:Hydrochloric Acid; D010100:Oxygen