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Simulation of the VUV Absorption Spectra of Oxygenates and Hydrocarbons: A Joint Theoretical–Experimental Study
[Image: see text] Vacuum UV absorption spectroscopy is regularly used to provide unambiguous identification of a target species, insight into the electronic structure of molecules, and quantitative species concentrations. As molecules of interest have become more complex, theoretical spectra have be...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10165657/ https://www.ncbi.nlm.nih.gov/pubmed/37097841 http://dx.doi.org/10.1021/acs.jpca.2c07743 |
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author | Bralick, Addison K. Mitchell, Erica C. Doner, Anna C. Webb, Annabelle R. Christianson, Matthew G. Turney, Justin M. Rotavera, Brandon Schaefer, Henry F. |
author_facet | Bralick, Addison K. Mitchell, Erica C. Doner, Anna C. Webb, Annabelle R. Christianson, Matthew G. Turney, Justin M. Rotavera, Brandon Schaefer, Henry F. |
author_sort | Bralick, Addison K. |
collection | PubMed |
description | [Image: see text] Vacuum UV absorption spectroscopy is regularly used to provide unambiguous identification of a target species, insight into the electronic structure of molecules, and quantitative species concentrations. As molecules of interest have become more complex, theoretical spectra have been used in tandem with laboratory spectroscopic analysis or as a replacement when experimental data is unavailable. However, it is difficult to determine which theoretical methodologies can best simulate experiment. This study examined the performance of EOM-CCSD and 10 TD-DFT functionals (B3LYP, BH&HLYP, BMK, CAM-B3LYP, HSE, M06-2X, M11, PBE0, ωB97X-D, and X3LYP) to produce reliable vacuum UV absorption spectra for 19 small oxygenates and hydrocarbons using vertical excitation energies. The simulated spectra were analyzed against experiment using both a qualitative analysis and quantitative metrics, including cosine similarity, relative integral change, mean signed error, and mean absolute error. Based on our ranking system, it was determined that M06-2X was consistently the top performing TD-DFT method with BMK, CAM-B3LYP, and ωB97X-D also producing reliable spectra for these small combustion species. |
format | Online Article Text |
id | pubmed-10165657 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-101656572023-05-09 Simulation of the VUV Absorption Spectra of Oxygenates and Hydrocarbons: A Joint Theoretical–Experimental Study Bralick, Addison K. Mitchell, Erica C. Doner, Anna C. Webb, Annabelle R. Christianson, Matthew G. Turney, Justin M. Rotavera, Brandon Schaefer, Henry F. J Phys Chem A [Image: see text] Vacuum UV absorption spectroscopy is regularly used to provide unambiguous identification of a target species, insight into the electronic structure of molecules, and quantitative species concentrations. As molecules of interest have become more complex, theoretical spectra have been used in tandem with laboratory spectroscopic analysis or as a replacement when experimental data is unavailable. However, it is difficult to determine which theoretical methodologies can best simulate experiment. This study examined the performance of EOM-CCSD and 10 TD-DFT functionals (B3LYP, BH&HLYP, BMK, CAM-B3LYP, HSE, M06-2X, M11, PBE0, ωB97X-D, and X3LYP) to produce reliable vacuum UV absorption spectra for 19 small oxygenates and hydrocarbons using vertical excitation energies. The simulated spectra were analyzed against experiment using both a qualitative analysis and quantitative metrics, including cosine similarity, relative integral change, mean signed error, and mean absolute error. Based on our ranking system, it was determined that M06-2X was consistently the top performing TD-DFT method with BMK, CAM-B3LYP, and ωB97X-D also producing reliable spectra for these small combustion species. American Chemical Society 2023-04-25 /pmc/articles/PMC10165657/ /pubmed/37097841 http://dx.doi.org/10.1021/acs.jpca.2c07743 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Bralick, Addison K. Mitchell, Erica C. Doner, Anna C. Webb, Annabelle R. Christianson, Matthew G. Turney, Justin M. Rotavera, Brandon Schaefer, Henry F. Simulation of the VUV Absorption Spectra of Oxygenates and Hydrocarbons: A Joint Theoretical–Experimental Study |
title | Simulation of the
VUV Absorption Spectra of Oxygenates
and Hydrocarbons: A Joint Theoretical–Experimental Study |
title_full | Simulation of the
VUV Absorption Spectra of Oxygenates
and Hydrocarbons: A Joint Theoretical–Experimental Study |
title_fullStr | Simulation of the
VUV Absorption Spectra of Oxygenates
and Hydrocarbons: A Joint Theoretical–Experimental Study |
title_full_unstemmed | Simulation of the
VUV Absorption Spectra of Oxygenates
and Hydrocarbons: A Joint Theoretical–Experimental Study |
title_short | Simulation of the
VUV Absorption Spectra of Oxygenates
and Hydrocarbons: A Joint Theoretical–Experimental Study |
title_sort | simulation of the
vuv absorption spectra of oxygenates
and hydrocarbons: a joint theoretical–experimental study |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10165657/ https://www.ncbi.nlm.nih.gov/pubmed/37097841 http://dx.doi.org/10.1021/acs.jpca.2c07743 |
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