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21 May 2014 Sensitive algorithm for multiple-excitation-wavelength resonance Raman spectroscopy
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Abstract
Raman spectroscopy is a widely used spectroscopic technique with a number of applications. During the past few years, we explored the use of simultaneous multiple-excitation-wavelengths (MEW) in resonance Raman spectroscopy. This approach takes advantage of Raman band intensity variations across the Resonance Raman spectra obtained from two or more excitation wavelengths. Amplitude variations occur between corresponding Raman bands in Resonance Raman spectra due to complex interplay of resonant enhancement, self-absorption and laser penetration depth. We have developed a very sensitive algorithm to estimate concentration of an analyte from spectra obtained using the MEW technique. The algorithm uses correlations and least-square minimization approach to calculate an estimate for the concentration. For two or more excitation wavelengths, measured spectra were stacked in a two dimensional matrix. In a simple realization of the algorithm, we approximated peaks in the ideal library spectra as triangles. In this work, we present the performance of the algorithm with measurements obtained from a dual-excitation-wavelength Resonance Raman sensor. The novel sensor, developed at WVHTCF, detects explosives from a standoff distance. The algorithm was able to detect explosives with very high sensitivity even at signal-to-noise ratios as low as ~1.6. Receiver operating characteristics calculated using the algorithm showed a clear benefit in using the dual-excitation-wavelength technique over single-excitation-wavelength techniques. Variants of the algorithm that add more weight to amplitude variation information showed improved specificity to closely resembling spectra.
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Balakishore Yellampalle, Hai-Shan Wu, William McCormick, Mikhail Sluch, Robert Martin, Robert Ice, and Brian E. Lemoff "Sensitive algorithm for multiple-excitation-wavelength resonance Raman spectroscopy", Proc. SPIE 9101, Next-Generation Spectroscopic Technologies VII, 91010P (21 May 2014); https://doi.org/10.1117/12.2050454
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