The spectroscopic
quantification of mixture compositions usually
requires pure compounds and mixtures of known compositions for calibration.
Since they are not always available, methods to fill such gaps have
evolved, which are, however, not generally applicable. Therefore,
calibration can be extremely challenging, especially when multiple
unstable species, for example, intermediates, exist in a system. This
study presents a new calibration approach that uses ab initio molecular dynamics (AIMD)-simulated spectra to set up and calibrate
models for the physics-based spectral analysis method indirect hard
modeling (IHM). To demonstrate our approach called AIMD–IHM,
we analyze Raman spectra of ternary hydrogen-bonding mixtures of acetone,
methanol, and ethanol. The derived AIMD–IHM pure-component
models and calibration coefficients are in good agreement with conventionally
generated experimental results. The method yields compositions with
prediction errors of less than 5% without any experimental calibration
input. Our approach can be extended, in principle, to infrared and
NMR spectroscopy and allows for the analysis of systems that were
hitherto inaccessible to quantitative spectroscopic analysis.
The spectroscopic quantification of mixture compositions usually requires pure compounds and mixtures of known composition for calibration. Since they are not always available, methods to fill such gaps have evolved, which are, however, not generally applicable. Therefore, calibration can be extremely challenging, especially when multiple instable species, e.g. intermediates, exist in a system. This study presents a new calibration approach that uses ab initio Molecular Dynamics (AIMD)-simulated spectra as to set up and calibrate models for the physics-based spectral analysis method Indirect Hard Modeling (IHM). To demonstrate our approach called AIMD-IHM, we analyze Raman spectra of ternary hydrogen-bonding mixtures of acetone, methanol, and ethanol. The derived AIMD-IHM pure-component models and calibration coefficients are in good agreement with conventionally generated experimental results. The method yields compositions with prediction errors of less than 5% without any experimental calibration input. Our approach can be extended, in principle, to IR and NMR spectroscopy and allows for the analysis of systems that were hitherto inaccessible to quantitative spectroscopic analysis.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.