Simulation of the VUV Absorption Spectra of Oxygenates and Hydrocarbons: A Joint Theoretical-Experimental Study

Overview

Journal J Phys Chem A

Publisher American Chemical Society

Specialty Chemistry

Date 2023 Apr 25

PMID 37097841

Authors

Addison K Bralick

Erica C Mitchell

Anna C Doner

Annabelle R Webb

Matthew G Christianson

Justin M Turney

Brandon Rotavera

Henry F Schaefer 3rd

Affiliations

Soon will be listed here.

Abstract

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.

Citing Articles

Evaluating the Importance of Conformers for Understanding the Vacuum-Ultraviolet Spectra of Oxiranes: Experiment and Theory.

Beck I, Mitchell E, Hill A, Turney J, Rotavera B, Schaefer 3rd H J Phys Chem A. 2024; 128(50):10906-10920.

PMID: 39641250 PMC: 11664588. DOI: 10.1021/acs.jpca.4c04391.

VUV absorption spectra of water and nitrous oxide by a double-duty differentially pumped gas filter.

Bodi A, Knurr J, Ascher P, Hemberger P, Bostedt C, Haddad A J Synchrotron Radiat. 2024; 31(Pt 5):1257-1263.

PMID: 39042580 PMC: 11371026. DOI: 10.1107/S1600577524005423.

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