Gaussian mixture model clustering algorithms for the analysis of high-precision mass measurements

TL;DR

This paper demonstrates that Gaussian mixture model clustering algorithms effectively analyze complex PI-ICR mass spectrometry data, improving spot detection accuracy and confirming measurements of specific isotopes.

Contribution

The paper introduces GMM clustering algorithms as an optimal method for analyzing PI-ICR data, outperforming other algorithms in handling noise and non-ideal data scenarios.

Findings

GMM algorithms outperform other clustering methods on simulated PI-ICR data.

GMM-based analysis yields isotope measurements consistent with published values.

GMM clustering improves the accuracy of ion spot detection in complex datasets.

Abstract

The development of the phase-imaging ion-cyclotron resonance (PI-ICR) technique for use in Penning trap mass spectrometry (PTMS) increased the speed and precision with which PTMS experiments can be carried out. In PI-ICR, data sets of the locations of individual ion hits on a detector are created showing how ions cluster together into spots according to their cyclotron frequency. Ideal data sets would consist of a single, 2D-spherical spot with no other noise, but in practice data sets typically contain multiple spots, non-spherical spots, or significant noise, all of which can make determining the locations of spot centers non-trivial. A method for assigning groups of ions to their respective spots and determining the spot centers is therefore essential for further improving precision and confidence in PI-ICR experiments. We present the class of Gaussian mixture model (GMM) clustering algorithms as an optimal solution. We show that on simulated PI-ICR data, several types of GMM clustering algorithms perform better than other clustering algorithms over a variety of typical scenarios encountered in PI-ICR. The mass spectra of $^{163}\text{Gd}$, $^{163m}\text{Gd}$, $^{162}\text{Tb}$, and $^{162m}\text{Tb}$ measured using PI-ICR at the Canadian Penning trap mass spectrometer were checked using GMMs, producing results that were in close agreement with the previously published values.