[Identification of the characteristic vibrations for 16 PAHs based on Raman spectrum]

In the present paper, by means of density functional theory in B3LYP/6-311++G(d, p) method, 16 kinds of pollutants, i. e. polycyclic aromatic hydrocarbons (PAHs): naphthalene (Nap), acenaphthylene (AcPy), acenaphthene (Acp), fluorene (Flu), phenanthrene (PA), anthracene (Ant), fluoranthene (Fl), pyrene (Pyr), benzo [a] anthracene (BaA), fused two naphthalene (CHR), benzo [b] fluoranthene (BbF), benzo [k] fluoranthene (BkF), benzo [a] pyrene (BaP), dibenzo (a, h) anthracene (DahA), dibenzo [g, h, i] pyrene (BghiP) and indene benzene (1, 2, 3-cd) pyrene (IcdP) among the U. S. EPA priority pollutants were selected, whose structures were optimized and Raman vibrational frequencies and depolarization were calculated. The structure, Raman vibrational frequencies and depolarization were basis of identification of PAHs. Studies have shown that Raman vibrations of 16 PAHs are mainly distributed in three frequency regions: 200-1 000 cm(-1) (fingerprint region), 1 000-1 700 cm(-1) and 3 000-3 200 cm(-1) (group frequency region), corresponding vibrations were assigned to ring deformation (ring def), C-C stretching (CCStr), C-H wiggle (CHw) and of these two patterns (CCStrCCw), and C-H stretching (CHStr). Further analysis showed that in fingerprint region the depolarization of 16 PAHs was reduced with the symmetry of benzene deformation vibration enhanced. At the point of minimum depolarization, symmetry and Raman peak of benzene ring breathing vibration were found strongest. At the minimum differential wave number the strongest peak in fingerprint region was distinguishable by micro-Raman spectroscopy. Therefore, 16 PAHs can be individually identified by depolarization and the strongest peak in fringerprint region. Vibration frequencies and peak intensity distribution of alkanes (Akn), olefin (Oe), alkyne (Aye), alcohols and phenols (Aap), aliphatic ether (Ape), arylalkyl ether (Aae), aldehydes (Ahd), ketones (Ktn), carboxylic acid (Cba), esters (Etr), amines (Aie), nitriles (Nte), amides (Aid), acid anhydride (Ahr), aromatic hydrocarbons (Ahc) were not completely consistent with each other, and interference can be discharged by the differences of frequency and peak intensity distribution.