Coherent anti-Stokes Raman Scattering; when difference between two frequencies matches frequency of particular molecular vibration, interaction

of laser beams and sample results in coherent vibrational motion of molecules, greatly enhancing the signals. Abstract: want to find potential correlations between absorption band and SERS activity of solution-based silver nanoparticles and morphology and size of silver nanoparticles. As particle size increases, SERS activity decreases. There is an optimal nanoparticle size at lambda = 390 nm at 15 nm, as SERS is strongest here. Goal: use UV-vis spectroscopy and High-res electron microscopy to study effects of size and max of Ag nanoparticles on SERS enhancement. Intro: Metal nanoparticles have strong absorption features or bands in the UV-vis regions of the EMS because of surface plasmons (SP). Raman-active molecules are adsorbed onto metal surfaces like Ag or Au, which gives an enhanced signal from 103 to 106 obtain molecular and structural info from trace amounts. We already know that: - increasing particle size causes a red shift in the SP band and that there was increased integrated peak area of the SP band, which could mean that theres aggregation. nanoparticle aggregation = broader SP band. Second band results from coupling of surface plasmons between aggregated particles and SERS activity rises b/c of this coupling. There is a critical size of Au nanoparticles needed for SERS activity. Adding a salt like NaCl is needed to see strong SERS signals, suggesting the Cl- ions alter the Ag surface in a way that produces more enhanced signal or that signals arise from clusters. (debate between chemical and electromagnetic enhancement in SERS). There is demand for understanding SERS properties in solution. Experimental methods: Synthesize Ag nanoparticles of various sizes. Prepare SERS samples. See morphological, optical and spectroscopic properties of Ag nanoparticles with UV-vis spectroscopy, and see nanoparticle size with STEM. Do SERS. Results and Discussion: Used Ag nanoparticles of varying sizes to find effect of size on SPR and SERS intensity. Van der Waals interactions are strongest force that causes aggregation of particles into large clusters, especially if the nanoparticles are small. For less than 15 nm solutions, aggregation continues and you have a large cluster that doesnt have buoyancy to remain in solution = decreased SERS activity. Increasing size of nanoparticle wavelength leads to broadening of the SP absorption band, indicating aggregation and larger particle size distributions. Hence, there is a direct comparison between the wavelengths of SP bands and nanoparticle size. After lambda of390 nm, SERS intensity decreases. Optimal wavelength is 390 nm. To maximize SERS intensity, you need moderate interparticle coupling between nanoparticles. As particle size increases, SERS activity decreases and max is shifted slightly. Conclusions: SERS activity is dependent on particle size and extent of aggregation. Shape of SP band and UV-vis are good indicators for these. Optimal SP wavelength is 390 nm. (Potential to use SP band as quick diagnostic tool to indicate SERS activity w/ solution based nanoparticles.