Vacuum-ultraviolet absorption cross-sections of functionalized four-carbon species

Doner, Anna C.; Webb, Annabelle R.; Dewey, Nicholas S.; Hartness, Samuel W.; Christianson, Matthew G.; Koritzke, Alanna L.; Larsson, Alexander; Frandsen, Kelsey M.; Rotavera, Brandon

doi:10.1016/j.jqsrt.2022.108346

Cited by 7 publications

(3 citation statements)

References 63 publications

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“…Vacuum ultraviolet (VUV) absorption spectroscopy is a powerful analytical tool that can probe high-energy valence electronic transitions (e.g., σ → σ* and n → σ*) and Rydberg transitions, which are common in hydrocarbons and oxygenates. − By accessing these transitions, a molecule’s VUV absorption spectrum allows the definitive detection of the target species, a more complete description of the species’ electronic structure, and quantitative, isomer-resolved speciation measurements. − Despite its applicability, experimental VUV spectroscopy does have limitations. Primarily, it requires the target molecule to be feasible to synthesize and isolate at sufficient yield and purity.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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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.

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Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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“…The UV absorption spectra of AcAc and other carbonyl-containing species are shown in Figure . ,− The AcAc spectrum is dominated by an intense structureless band centered at 263 nm, accompanied by a much weaker feature at ∼295 nm. The strong UV absorption of AcAc has been attributed to excitation of the S 2 (ππ*) state of enol-AcAc, with the weaker feature attributed to the S 1 (nπ*) state of keto-AcAc. , Electron-impact spectroscopy measurements have also identified a weak spin-forbidden band at 347 nm .…”

Section: Introductionmentioning

confidence: 99%

“…UV absorption spectra for acetylacetone (AcAc), acetone, and MVK. Data obtained from various sources. ,− …”

Section: Introductionmentioning

confidence: 99%

Acetylacetone Photolysis at 280 nm Studied by Velocity-Map Ion Imaging

Rinaman

Murray

2023

J. Phys. Chem. A

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The photolysis of acetylacetone (AcAc) has been studied using velocity-map ion imaging with pulsed nanosecond lasers. The enolone tautomer of AcAc (CH3C(O)CHC(OH)CH3) was excited in the strong UV absorption band by UV pulses at 280 nm, preparing the S2(ππ*) state, and products were probed after a short time delay by single-photon VUV ionization at 118.2 nm. Two-color UV + VUV time-of-flight mass spectra show enhancement of fragments at m/z = 15, 42, 43, 58, and 85 at the lowest UV pulse energies and depletion of the parent ion at m/z = 100. Ion images of the five major fragments are all isotropic, indicating dissociation lifetimes that are long on the timescale of molecular rotation but shorter than the laser pulse duration (<6 ns). The m/z = 15 and 85 fragments have identical momentum distributions with moderate translational energy release, suggesting that they are formed as a neutral product pair and likely via a Norrish type I dissociation of the enolone to form CH3 + C(O)CHC(OH)CH3 over a barrier on a triplet surface. The m/z = 43 fragment may be tentatively assigned to the alternative Norrish type I pathway that produces CH3CO + CH2C(O)CH3 on S0 following phototautomerization to the diketone, although alternative mechanisms involving dissociative ionization of a larger primary photoproduct cannot be conclusively ruled out. The m/z = 42 and 58 fragments are not momentum-matched and consequently are not formed as a neutral pair via a unimolecular dissociation pathway on S0. They also likely originate from the dissociative ionization of primary photofragments. RRKM calculations suggest that unimolecular dissociation pathways that lead to molecular products on S0 are generally slow, implying an upper-limit lifetime of <46 ns after excitation at 280 nm. Time-dependent measurements suggest that the observed photofragments likely do not arise from dissociative ionization of energized AcAc S0*.

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Differences in the Modification Effect in the Depth Direction on the Surface of Epoxy Resin Irradiated with Vacuum Ultraviolet Light

Endo,

Ishikawa,

Shirakashi

et al. 2024

J. Electron. Mater.

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Vacuum-ultraviolet absorption cross-sections of functionalized four-carbon species

Cited by 7 publications

References 63 publications

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

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

Acetylacetone Photolysis at 280 nm Studied by Velocity-Map Ion Imaging

Differences in the Modification Effect in the Depth Direction on the Surface of Epoxy Resin Irradiated with Vacuum Ultraviolet Light

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