Analytical Chemistry

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

Authors

  • Justus Wöhl Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany ,
  • Wassja Kopp Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany ,
  • Iryna Yevlakhovych Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany ,
  • Leo Bahr Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany ,
  • Hans-Jürgen Koß Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany ,
  • Kai Leonhard Institute of Technical Thermodynamics, RWTH Aachen University, 52052 Aachen, Germany

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.

Content

Thumbnail image of AIMDIHM.pdf

Supplementary material

Thumbnail image of SI-AIMDIHM.pdf
Supplementary Information for “Completely computational model setup for spectroscopic techniques: the ab initio molecular dynamics indirect hard modeling (AIMD-IHM) approach”
Supplementary Material with details on AIMD-IHM software use, simulation length study, experimental data and hard models.
Thumbnail image of Spectra.zip
Raw data files listed in SI document
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