The covariance of count-conserving rebinned Raman channels records the shared noise created when one measured channel contributes to several output channels. For a fixed deterministic rebinning matrix and an input count vector with covariance matrix , the output is andThis identity needs finite second moments, not a Gaussian approximation. Raman spectral rebinning with conserved integrated counts describes the count-preserving map; retaining its full covariance matrix is necessary for uncertainties of sums and fitted spectral features.[ref]
Consider independent input counts with means and and Poisson distribution variances equal to those means. Split them deterministically usingThe three output means are . Their total has variance , exactly the original total variance, and standard deviation . Keeping only diagonal entries would give variance and standard deviation about , understating the uncertainty of the conserved total.
The rank deficiency from deterministic spectral upsampling is visible without matrix inversion: the vector has zero output contrast for every possible input. Three displayed channels therefore contain at most two independent degrees of freedom in this model. Fractional redistribution creates correlated numerical channels; it is different from physically assigning each detected photon randomly to one new channel.
The primary stimulated-Raman apparatus records spectra with array detectors and calibrates their spectral coordinates.[ref]
Femtosecond Broadband Stimulated Raman: A New Approach for High-Performance Vibrational Spectroscopy by David W. McCamant and others. Instrumentation, array detection and frequency-shift calibration; Data Collection, equation 4
When those data are placed on a new spectral grid, the original detector counts remain the source of statistical information. Additional interpolation points do not supply independent photon measurements.Spectral-density conversion between wavelength and Raman shift preserves the integrated physical quantity while changing its horizontal coordinate. Fix the excitation wavelength , and let be the Raman shift. Using numerical vacuum wavelengths in nanometres and shifts in ,Let denote detected counts per nanometre and counts per unit Raman shift. Conservation of counts under a change of variables givesThe conversion factor carries the corresponding density-unit change. The same argument applies to calibrated power densities, provided both sides describe the same quantity.
For an original narrow bin centred at , a count density of per nanometre becomes per . A one-nanometre bin there spans approximately , so its integrated count remains about . At , the same wavelength density becomes per . Relabeling bin positions without adjusting the density would conceal this coordinate dependence.
For finite bins, use their exact transformed edges and preserve each bin's integral. Raman spectral rebinning with conserved integrated counts distinguishes this operation from interpolating peak heights onto a new grid. Instrument response correction is another step; the Jacobian alone does not calibrate detector sensitivity or remove background.
The primary FSRS apparatus calibrated Raman shifts using known solvent lines and dispersed the probe spectrum onto an array.[ref]
Femtosecond Broadband Stimulated Raman: A New Approach for High-Performance Vibrational Spectroscopy by David W. McCamant and others. Instrumentation/Figure 2, spectral detection and absolute-shift calibration
Its dimensionless Raman pump-on pump-off gain ratio is a different observable: a ratio of matched spectral densities can cancel their common coordinate factor. It should not be treated as a count density merely because it is plotted against Raman shift.