Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing AnalogtoDigital 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 analogtodigital 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 “pulsepeak 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:

^{[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):
 PNNLSA124906
Journal ID: ISSN 00032700; 453040220
 Grant/Contract Number:
 AC0576RL01830; MR/J013994/1
 Type:
 Accepted Manuscript
 Journal Name:
 Analytical Chemistry
 Additional Journal Information:
 Journal Volume: 89; Journal Issue: 4; Journal ID: ISSN 00032700
 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
Ipsen, Andreas. Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing AnalogtoDigital Converters and Electron Multipliers. United States: N. p.,
Web. doi:10.1021/acs.analchem.6b02446.
Ipsen, Andreas. Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing AnalogtoDigital Converters and Electron Multipliers. United States. doi:10.1021/acs.analchem.6b02446.
Ipsen, Andreas. 2017.
"Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing AnalogtoDigital Converters and Electron Multipliers". United States.
doi:10.1021/acs.analchem.6b02446. https://www.osti.gov/servlets/purl/1353320.
@article{osti_1353320,
title = {Derivation of the Statistical Distribution of the Mass Peak Centroids of Mass Spectrometers Employing AnalogtoDigital Converters and Electron Multipliers},
author = {Ipsen, Andreas},
abstractNote = {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 analogtodigital 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 “pulsepeak 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.},
doi = {10.1021/acs.analchem.6b02446},
journal = {Analytical Chemistry},
number = 4,
volume = 89,
place = {United States},
year = {2017},
month = {2}
}