Surface enhanced Raman vibrational studies at solid/gas by I. Pockrand

By I. Pockrand

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3). The l i n e at 1026 cm- I is quite strong in SER spectra from pyridine on activated s i l v e r electrodes for potentials positive (~ I V) to the point of zero charge /57, 247/. Here i t has t e n t a t i v e l y been assigned to Lewis-coordinated pyridine /57/ or adsorbed pyridinium cations PyH+ /246/. Table 2 summarizes the pyridine SER l i n e energies and i n t e n s i t i e s . The mode sel e c t i v e enhancement is c l e a r l y seen when comparing A1 mode i n t e n s i t i e s of surface pyridine (column e) and neat pyridine (column a).

E . of surface pyridine. The c o n t r i b u t i o n s of the various processes to the i n t e n s i t y v a r i a t i o n of SER signals with temperature are discussed in Sects. 4. 1,4 Excitation Spectra Raman e x c i t a t i o n spectra are p a r t i c u l a r l y useful to elaborate various contributions to SERS. They may provide information on the intermediate e l e c t r o n i c states of the scattering process as well as on the surface topography of the metal via the local f i e l d strength which a f f e c t s the Raman scattered i n t e n s i t y .

A f t e r /358/ 29 specific e x c i t a t i o n p r o f i l e s for surface enhanced Raman scattering (see Sect. 4). A close look at the SER spectra allows the following statements: i) Almost a l l pyridine skeletal fundamentals are observed and can be assigned /99, 108,119/. There i s , however, no indication of a metal-pyridine stretching v i b r a t i o n /108/. ii) Several low energy features at 73 cm-1, 112 cm-1, and 161 cm-1 (Fig. I0) re- f l e c t an i n t r i n s i c property of coldly evaporated s i l v e r films.

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