title: Structure and IR spectra of microhydrated Cl2 with an excess electron: experiment versus theory.
abstract: A working methodology to generate theoretical IR spectra following ab initio electronic structure methods is reported. Theoretical IR spectra of Cl(2)(•-)·nH(2)O clusters (n = 1-5) are generated as a case study. Excellent agreement between the calculated and the reported experimental IR spectra based on size-selected spectroscopy is observed. It is shown that uniform scaling of calculated harmonic frequencies of these hydrated clusters fail to produce accurate IR spectra. Two different scaling factors in two different regions of O-H stretching of solvent water molecules are needed to account for the anharmonic contribution. This observation is also true for Br(2)(•-)·nH(2)O and I(2)(•-)·nH(2)O systems.
authors: Theoretical Chemistry Section, Chemistry Group, Bhabha Atomic Research Centre, Mumbai, India. akpathak@barc.gov.in
authors: A K
authors: AK
authors: Pathak
authors: T
authors: T
authors: Mukherjee
authors: D K
authors: DK
authors: Maity
mesh_terms: D002712:Chlorides / Q000737:chemistry*; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry; D015394:Molecular Structure; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared
chemical_list: D002712:Chlorides; D005609:Free Radicals