title: Solvation of LiClO4 and NaClO4 in deuterated acetonitrile studied by means of infrared and Raman spectroscopy.
abstract: Vibrational characteristics of CD3CN solutions of LiClO4 and NaClO4 have been studied by means of infrared and Raman spectroscopy. Blue shifts of 22 and 11 cm(-1) of the v2 C[triple bond]N stretch are observed resulting from interaction of CD3CN with Li+ and Na+, respectively. The number of primary solvation sites of both Li+ and Na+ in acetonitrile is believed to be four from the comparison of the Raman intensities of the C[triple bond]N stretch for free CD3CN and those coordinated to Li+ and Na+. Evidently formation of contact ion pairs of the cation (Li+ or Na+) and anion (ClO4-) is more probable at a higher concentration of the salt. The characteristics of the v2 C[triple bond]N stretch, v4 C-C stretch, and v8 CCN deformation bands vary substantially upon coordination, while other vibrational bands are relatively immune to the donor-acceptor interaction. DFT calculations have also been performed at the BLYP/6-31 + G(2d,p) level to examine the structures and vibrational characteristics of CD3CN coordinated to Li+ and Na+. The calculated results are in good agreement with the observed vibrational characteristics.
authors.affiliation: Department of Chemistry, University of Incheon, Nam-ku, South Korea.
authors.forename: Jun-Sik
authors.initials: JS
authors.lastname: Seo
authors.forename: Byeong-Seo
authors.initials: BS
authors.lastname: Cheong
authors.forename: Han-Gook
authors.initials: HG
authors.lastname: Cho
mesh_terms: D000097:Acetonitriles / Q000737:chemistry*; D003903:Deuterium; D018020:Lithium Compounds / Q000737:chemistry*; D015394:Molecular Structure; D010472:Perchlorates / Q000737:chemistry*; D017670:Sodium Compounds / Q000737:chemistry*; D012997:Solvents; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D014732:Vibration
chemical_list: D000097:Acetonitriles; D018020:Lithium Compounds; D010472:Perchlorates; D017670:Sodium Compounds; D012997:Solvents; C031068:sodium perchlorate; D003903:Deuterium; C054684:lithium perchlorate; C032159:acetonitrile