By Noyes W
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Extra resources for Advances in Photochemistry
Fig. 8 shows how much the local ﬁeld varies for truncated tetrahedron particles, but an important question is how the ﬁeld changes when other particle shapes are considered. Fig. 10 shows local ﬁeld contours for several other particle shapes including a sphere, cylinder, cube, prism, and untruncated tetrahedron. This shows the peak ﬁeld can vary a lot, with the smallest lEl2 occurring for a sphere (less than 102), and the largest for particles with sharp tips (104 for the tetrahedron). These lEl2 values provide an important estimate of the intensity enhancement expected in single molecule SERS enhancements, as the electromagnetic contribution to this intensity is approximately equal to the peak value of the product lEðvÞl2 lEðv0 Þl2 where v is the incident frequency and v0 is the Stokes frequency.
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Since the plasmon peaks are usually somewhat broader than the shift between v and v0 ; the intensity enhancement is approximately lEl4 : Thus if lEl2 is approximately 104, the Raman intensity enhancement is close to 108. This may seem to be a large number, but in fact estimates of this enhancement based on single molecule SERS measurements are much larger (1012 – 1015) [9,38,51 –55]. One issue in the comparison of theory and experiment for single molecule SERS is that the experiments have mostly been done for aggregates of particles.
Advances in Photochemistry by Noyes W