A Raman spectrum records the strength of Raman scattering as a function of scattered optical frequency or, usually, Raman shift relative to the excitation. For vacuum wavelengths in nanometres, a common wavenumber convention isHere the numerical wavelengths are in nanometres. Stokes Raman scattering has positive shift under this convention; Anti-Stokes Raman scattering has negative shift. The strong unshifted Rayleigh scattering line is not a vibrational Raman band.
For an original chosen excitation and a vibration, the Stokes wavenumber is , giving . The corresponding anti-Stokes wavelength is . Changing the excitation changes these optical wavelengths while the same assumed transition retains its Raman shift. The One-mode Raman spectrum example gives an existing level diagram and a separate numerical spectrum.
The vertical quantity must be stated too: detector counts per spectral bin, calibrated scattered power density and a stimulated gain ratio are different observables. Femtosecond stimulated Raman spectroscopy can plot the Raman pump-on pump-off gain ratio rather than spontaneous photon counts. Its primary apparatus disperses probe and reference beams onto an array and calibrates shifts with known solvent lines.[ref]
Femtosecond Broadband Stimulated Raman: A New Approach for High-Performance Vibrational Spectroscopy by David W. McCamant and others. Materials and Methods, Instrumentation/Figure 2 and absolute-shift calibration; Data Collection, equation 4
Spectral-density conversion between wavelength and Raman shift also changes the density's units: rebadging the horizontal axis alone need not preserve a spectral integral. Background, excitation rejection, instrument response and spectral resolution affect observed band heights and widths. An integrated band area is not determined by peak height alone. A chemical inference should compare calibrated positions and responses under specified conditions, rather than identify a material from one unqualified peak.
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