title: FT-IR spectroscopy combined with DFT calculation to explore solvent effects of vinyl acetate.
abstract: The infrared vibration frequencies of vinyl acetate (VAc) in 18 different solvents were theoretically computed at Density Function Theory (DFT) B3LYP/6-311G(*) level based on Polarizable Continuum Model (PCM) and experimentally recorded by FT-IR spectroscopy. The solvent-induced long-range bulk electrostatic solvation free energies of VAc (ΔGelec) were calculated by the SMD model. The C=O stretching vibration frequencies of VAc were utilized as a measure of the chemical reactivities of the CC group in VAc. The calculated and experimental C=O stretching vibration frequencies of VAc (νcal(C=O) and νexp(C=O)) were correlated with empirical solvent parameters including the KBM equation, the Swain equation and the linear solvation energy relationships (LSER). Through ab initio calculation, assignments of the two C=O absorption bands of VAc in alcohol solvents were achieved. The PCM, SMD and ab initio calculation offered supporting evidence to explain the FT-IR experimental observations from differing aspects.
authors.affiliation: Department of Chemistry, Zhejiang University, Zheda Road No. 38, Hangzhou 310027, PR China.
authors.forename: Yi
authors.initials: Y
authors.lastname: Chen
authors.affiliation: Department of Chemistry, Zhejiang University, Zheda Road No. 38, Hangzhou 310027, PR China.
authors.forename: Hui
authors.initials: H
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, Zhejiang University, Zheda Road No. 38, Hangzhou 310027, PR China. Electronic address: liuqing@zju.edu.cn.
authors.forename: Qing
authors.initials: Q
authors.lastname: Liu
mesh_terms: D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D012997:Solvents; D014753:Vinyl Compounds; C011566:vinyl acetate
keywords: Ab initio; DFT; FT-IR; PCM; Solvent effects; Vinyl acetate