A perceived paucity of quantitative studies in the modern era of voltammetry: prospects for parameterisation of complex reactions in Bayesian and machine learning frameworks

A Comparison of Bayesian Inference Strategies for Parameterisation of Large Amplitude AC Voltammetry Derived from Total Current and Fourier Transformed Versions

“…However, methods and protocols for reliably solving the inverse problem in a statistical framework still need significant investigation. [53,66] This work confirms that Bayesian inference approaches are powerful, but need to be implemented with caution. Indeed their automated introduction without careful scrutiny of the fidelity of parameters recovered is fraught with danger.…”

“…When employing the heuristic method, an experienced experimenter has the opportunity to introduce intelligence based thinking into the data analysis. This form of dynamic intelligence is not available in mathematical forms of optimisation or Bayesian inference as implemented in this paper, although biasing the outcome in a preferable direction via smart application of the correct log‐likelihood is possible [42] and in the future machine learning could be introduced for this purpose [53,66] . In practice, the heuristic method only provides a single point parameter estimate, does not report the system reproducibility and is so tedious that only about three parameters can be varied and compared in a series of simulations where comparisons with experimental data are made via visual inspection.…”

“…This form of dynamic intelligence is not available in mathematical forms of optimisation or Bayesian inference as implemented in this paper, although biasing the outcome in a preferable direction via smart application of the correct log-likelihood is possible [42] and in the future machine learning could be introduced for this purpose. [53,66] In practice, the heuristic method only provides a single point parameter estimate, does not report the system reproducibility and is so tedious that only about three parameters can be varied and compared in a series of 5 in rows 3 and 6 respectively. Application of MLE-TCDS with Inference method could not be reliably fit for D and R u so other parameters were then fitted using experimental or literature values as described in the text.…”

Essay for the Rosarium Philosophicum on Electrochemistry Electrochemical Analysis – What it was, is, and Possibly will be

“…Examples are age determinations of metals, [32] and archeometric applications [33,34,35,36] . Another research field with great potential is the application of chemometry to electroanalysis, [37] and the most modern methods of machine learning as recently suggested by Bond [38] …”

“…[33,34,35,36] Another research field with great potential is the application of chemometry to electroanalysis, [37] and the most modern methods of machine learning as recently suggested by Bond. [38] The authors of this Rosarium Philosophorum on Electrochemistry have been instructed to write their essays in such way, "that this compilation will become a powerful reference, not only for scientists, engineers and corporate decision makers, but also for administrators in universities, decision Essays makers of funding agencies, and even journalists and politicians." Hence, I feel obliged to turn my voice to the people listed in the second part of this sentence.…”