Refining the thermochemical properties of CF, SiF, and their cations by combining photoelectron spectroscopy, quantum chemical calculations, and the Active Thermochemical Tables approach

Jacovella, Ugo; Ruscic, Branko; Chen, Ning L.; Le, Hai-Linh; Boyé-Péronne, Séverine; Hartweg, Sebastian; Chowdhury, Madhusree Roy; Garcia, Gustavo A.; Loison, Jean-Christophe; Gans, Bérenger

doi:10.1039/d3cp04244h

Cited by 2 publications

(1 citation statement)

References 99 publications

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“…The modeling indicates that the temperature of acetaldehyde is approximately at 270 K, in line with previous studies on the same setup which show rotational/translational temperatures of this order. [30,42,43] For the lowest-energy decomposition channel, responsible for the hydrogen atom loss, the AE 0K (CH 3 CO + ) is determined at 10.89 � 0.01 eV, agreeing well with the theoretically predicted energy of [2] � at 10.96 eV. In parallel with the decrease of the H loss channel, the fraction of the HCO + fragment ion increases quickly with the photon energy since the CH 3 loss channel is kinetically more favorable than the H loss.…”

Section: Breakdown Diagram and Dissociative Ionization Mechanismmentioning

confidence: 99%

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0–13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy

Wu,

Zhang,

et al. 2024

ChemPhysChem

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Photoionization and dissociative photoionization of acetaldehyde (CH3CHO) in the 10.0‒13.7 eV energy range are studied by using synchrotron radiation double imaging photoelectron photoion coincidence spectroscopy (i2PEPICO). The X2A' and A2A" electronic states of CH3CHO+ as well as the Franck‐Condon gap region between these two states have been populated with several vibrational sequences and assigned in the high‐resolution slow photoelectron spectrum (SPES). The adiabatic ionization energies (AIEs) of the X2A' and A2A" states are measured at 10.228 ± 0.006 and 12.52 ± 0.05 eV, respectively. The present results show that the X2A' state is a stable state while the A2A" state is fully dissociative to produce CH3CO+, CHO+ and CH4+ fragment ions. The 0K appearance energies (AE0K) of CH3CO+ and CHO+ fragment ions are determined through the modeling of the breakdown diagram, i.e., AE0K(CH3CO+) = 10.89 ± 0.01 eV (including a reverse barrier of ~ 0.19 eV) and AE0K(CHO+) = 11.54 ± 0.05 eV. In addition, the dissociation mechanisms of CH3CHO+ including statistical dissociation, direct bond breaking and isomerization are discussed with the support of the calculated dissociation limits and transition state energies.

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Section: Breakdown Diagram and Dissociative Ionization Mechanismmentioning

confidence: 99%

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0–13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy

Wu,

Zhang,

et al. 2024

ChemPhysChem

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Experimental characterization of SiCH+via single-photon ionization of gas-phase SiCH

Chen,

Gans,

Boyé-Péronne

et al. 2024

The Journal of Chemical Physics

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SiCH and its cation have consistently emerged as predicted species in models of silicon chemistry within the interstellar medium, although they remain unobserved in space. Hindered by their intrinsic instability, no spectroscopic insights have been gleaned concerning the SiCH+ cation. In this study, we present experimental measurements on the SiCH+ cation through single-photon ionization spectroscopy of the SiCH radical within the 8.0–11.0 eV range. Gas-phase SiCH radicals were generated through chemical reactions involving CHx (x = 0–3) and SiHy (y = 0–3) within a microwave discharge flow-tube reactor. Employing a double imaging photoelectron/photoion coincidence spectrometer on the DESIRS beamline at the SOLEIL synchrotron, we recorded mass-selected ion yield and photoelectron spectra. From the analysis of the photoelectron spectrum supported by ab initio calculations and Franck–Condon simulations, the adiabatic ionization energies for the transitions from the X2Π ground electronic state of SiCH toward the X+3Σ− and A+3Π electronic states of SiCH+ have been derived [8.935(6) and 10.664(6) eV, respectively, without spin–orbit correction]. The contribution from the less stable isomer HSiC has been explored in our analysis and ruled out in our experiments.

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Refining the thermochemical properties of CF, SiF, and their cations by combining photoelectron spectroscopy, quantum chemical calculations, and the Active Thermochemical Tables approach

Abstract: Thanks to combined ab initio calculations and experimental photoelectron studies of CF and SiF fluorinated radicals in the gas-phase, the thermochemical network of Active Thermochemical Tables was updated for these species and their cations.

Cited by 2 publications

References 99 publications

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0–13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy

Photoionization and Dissociative Photoionization of Acetaldehyde in the 10.0–13.7 eV Range by Synchrotron Photoelectron Photoion Coincidence Spectroscopy

Experimental characterization of SiCH+via single-photon ionization of gas-phase SiCH

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