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Theoretical elucidation of the origin of surface‐enhanced Raman spectra of PCB52 adsorbed on silver substrates
Author(s) -
Pan WenXiao,
Lai YongChao,
Wang RuoXi,
Zhang DongJu,
Zhan JinHua
Publication year - 2014
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.4421
Subject(s) - raman spectroscopy , raman scattering , density functional theory , chemistry , adsorption , molecule , spectral line , analytical chemistry (journal) , resonance (particle physics) , computational chemistry , atomic physics , optics , chromatography , physics , astronomy , organic chemistry
To better understand experimentally observed surface‐enhanced Raman Scattering (SERS) of polychlorinated biphenyls (PCBs) adsorbed on nanoscaled silver substrates, a systematic theoretical study was performed by carrying out density functional theory and time‐dependent density functional theory calculations. 2,2′,5,5′‐tetrachlorobiphenyl (PCB52) was chosen as a model molecule of PCBs, and Ag n ( n = 2, 4, 6, and 10) clusters were used to mimic active sites of substrates. Calculated normal Raman spectra of PCB52–Ag n ( n = 2, 4, 6, and 10) complexes are analogical in profile to that of isolated PCB52 with only slightly enhanced intensity. In contrast, the corresponding SERS spectra calculated at adopted incident light are strongly enhanced, and the calculated enhancement factors are 10 4 ~ 10 5 . Thus, the experimentally observed SERS phenomenon of PCBs supported on Ag substrates should correspond to the SERS spectra rather than the normal Raman spectra. The dominant enhancement in Raman intensities origins from the charge transfer resonance enhancement between the molecule and clusters. Copyright © 2014 John Wiley & Sons, Ltd.