Completely computational model setup for spectroscopic techniques: the ab initio molecular dynamics indirect hard modeling (AIMD-IHM) approach

03 January 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

quantitative mixture analysis
model-based calibration
TRAVIS
spectral simulation
missing-PCS
aixcalibration

Supplementary materials

Title
Description
Actions
Title
Supplementary Information for “Completely computational model setup for spectroscopic techniques: the ab initio molecular dynamics indirect hard modeling (AIMD-IHM) approach”
Description
Supplementary Material with details on AIMD-IHM software use, simulation length study, experimental data and hard models.
Actions
Title
Raw data files listed in SI document
Description
For pure components: Methanol: PCS/Experiment/MeOH-1300-6s-10x.wdf_0001.csv Ethanol: PCS/Experiment/EtOH-1300-4s-10x.wdf_0001.csv Acetone: PCS/Experiment/Ac-1300-2s-10x.wdf_0001.csv For mixtures: Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-15s-10x-Mix1.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-15s-10x-Mix2.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-10s-10x-Mix3.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-5s-10x-Mix4.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-15s-10x-Mix5.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-7s-10x-Mix6.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-10s-10x-Mix7.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-10s-10x-Mix8.wdf_0001summed.csv Ternary/Experiment/2021-03-08_Ac-MeOH-EtOH-532-1300-10s-10x-Mix9.wdf_0001summed.csv
Actions

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.