Window-capture sensitivity to mass offset

Window-capture sensitivity to mass offset describes how the extracted-ion window capture fraction changes when an ion peak shifts relative to a fixed extracted ion mass window. The shift is in the reported mass coordinate; it can change the selected signal even if the target's total peak area is constant.

For a normalized peak shape $p(m-\delta )$ with offset $\delta$ and window boundaries $a,b$, writeDifferentiation givesThe first-order response is determined by the signal density at the two boundaries. A symmetric peak centered in a symmetric window has equal boundary densities and hence zero first derivative. Zero first derivative does not mean perfect immunity: finite offsets can still reduce capture.

For an original Gaussian function model with standard deviation $\sigma$ and half-width $w$, let $\varphi$ and $\Phi$ be the standard normal density and standard normal cumulative distribution function. ThenFor small offsets the leading loss is consequently quadratic:With $w=2\sigma$, the exact capture is 0.9545 at zero offset and 0.9270 at $\delta =0.5\sigma$. The quadratic approximation gives 0.9275, close for this stipulated displacement. At the boundary $\delta =2\sigma$, capture is about 0.5000 and a small-offset approximation is no longer appropriate.

An experimental check can re-extract the same recorded spectra with deliberately shifted windows while retaining the same time limits and extracted-ion chromatogram baseline. This isolates a software-selection effect. IUPAC's selected-mass profile definition supplies the measurement setting, rather than a claim that all instruments have Gaussian peaks.^[ref] Wider windows may reduce target losses but admit interfering ions; mass resolving power and instrument calibration remain separate instrumental considerations.