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Title: Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing Analog-to-Digital Converters and Electron Multipliers

Here, the mass peak centroid is a quantity that is at the core of mass spectrometry (MS). However, despite its central status in the field, models of its statistical distribution are often chosen quite arbitrarily and without attempts at establishing a proper theoretical justification for their use. Recent work has demonstrated that for mass spectrometers employing analog-to-digital converters (ADCs) and electron multipliers, the statistical distribution of the mass peak intensity can be described via a relatively simple model derived essentially from first principles. Building on this result, the following article derives the corresponding statistical distribution for the mass peak centroids of such instruments. It is found that for increasing signal strength, the centroid distribution converges to a Gaussian distribution whose mean and variance are determined by physically meaningful parameters and which in turn determine bias and variability of the m/z measurements of the instrument. Through the introduction of the concept of “pulse-peak correlation”, the model also elucidates the complicated relationship between the shape of the voltage pulses produced by the preamplifier and the mean and variance of the centroid distribution. The predictions of the model are validated with empirical data and with Monte Carlo simulations.
Authors:
ORCiD logo [1]
  1. Swansea Univ., Swansea, Wales (United States). College of Medicine, Inst. of Mass Spectrometry; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Biological Sciences Division
Publication Date:
Report Number(s):
PNNL-SA-124906
Journal ID: ISSN 0003-2700; 453040220
Grant/Contract Number:
AC05-76RL01830; MR/J013994/1
Type:
Accepted Manuscript
Journal Name:
Analytical Chemistry
Additional Journal Information:
Journal Volume: 89; Journal Issue: 4; Journal ID: ISSN 0003-2700
Publisher:
American Chemical Society (ACS)
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
97 MATHEMATICS AND COMPUTING
OSTI Identifier:
1353320