Understanding Metal-Adsorbate Binding with Surface-Enhanced Raman Spectroscopy: Theory and Experiment*

Building on recent work [1], we use a combination of density functional theory (DFT) calculations and surface-enhanced Raman spectroscopy (SERS) measurements to explain experimentally observed variations in SERS data of an organic molecule, trans-1,2-two (4-pyridyl) ethylene (BPE). For the BPE on Au surfaces, our DFT calculations provide a quantitative description of chemical enhancement (CE), and elucidate that variations reported in experiments arise from a convolution of two factors: a nonuniform frequency dependent electromagnetic enhancement, and dependence of CE on the sample incubation time. The later reveals aspects of the binding kinetics of BPE to Au surfaces.\\[4pt] [1] A. T. Zayak,et. al., arXiv:1011.1873v1