title: Effects of hydrogen bond and solvent polarity on the C=O stretching of bis(2-thienyl)ketone in solution.
abstract: The optimized structural parameters, the absorption and the resonance Raman spectra have been investigated for the bis(2-thienyl)ketone in gas phase, in cyclohexane, methanol, and acetonitrile solvents by means of time dependent density functional theory calculations, the solvent electronic polarization effect on the solvation shift is examined and in well accordance with the calculation. The effect of increasing the polarity of the solvent is well represented by the polarizable continuum model, both for the absorption spectra and resonance Raman intensities. The Raman spectra of the C=O stretching mode, which is sensitive to the intermolecular interaction for bis(2-thienyl)ketone dissolved in solvents, were systematically studied. It was found that the hydrogen bond effect plays an important role in reducing the carbonyl stretching wavenumbers. The results of Raman shifts were interpreted through the dilution effect, solvation effects, and hydrogen bond-forming effects. Furthermore, the excitation profiles of several important Raman bands of bis(2-thienyl)ketone molecule in different solvents have been critically analyzed. The solvent effects on structural and symmetry properties of the molecule in S2 electronic state as well as the short-time photo relaxation dynamics have been discussed.
authors.affiliation: Department of Chemistry and State Key Laboratory of Advanced Textiles Materials and Manufacture Technology, MOE, Zhejiang Sci-Tech University, Hangzhou 310018, China. zdwhg@163.com
authors.forename: Huigang
authors.initials: H
authors.lastname: Wang
authors.forename: Libo
authors.initials: L
authors.lastname: Wang
authors.forename: Shaosong
authors.initials: S
authors.lastname: Shen
authors.forename: Wenfei
authors.initials: W
authors.lastname: Zhang
authors.forename: Mingde
authors.initials: M
authors.lastname: Li
authors.forename: Lili
authors.initials: L
authors.lastname: Du
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng
authors.forename: David Lee
authors.initials: DL
authors.lastname: Phillips
mesh_terms: D000097:Acetonitriles / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D003510:Cyclohexanes / Q000737:chemistry; D005740:Gases / Q000737:chemistry; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry*; D000432:Methanol / Q000737:chemistry; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry; D012996:Solutions / Q000737:chemistry*; D013059:Spectrum Analysis, Raman
chemical_list: D000097:Acetonitriles; D003510:Cyclohexanes; D005740:Gases; D007659:Ketones; D012996:Solutions; C506365:Cyclohexane; D002244:Carbon; D010100:Oxygen; D000432:Methanol; C032159:acetonitrile