Title :

Accounting for molecular flexibility in photoionization: case of tert-butyl hydroperoxide

Author(s) :

Bourgalais, Jérémy [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Jiang, Zhongming [Auteur]
Scuola Normale Superiore di Pisa [SNS]
Bloino, Julien [Auteur]
Scuola Normale Superiore di Pisa [SNS]
Herbinet, Olivier [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Carstensen, Hans-Heinrich [Auteur]
Fundación Agencia Aragonesa para la Investigación y el Desarrollo [ARAID]
95355|||University of Zaragoza - Universidad de Zaragoza [Zaragoza]
Garcia, Gustavo A. [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Arnoux, Philippe [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Tran, Luc-Sy [Auteur]
Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Vanhove, Guillaume [Auteur]
Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522
Nahon, Laurent [Auteur]
Synchrotron SOLEIL [SSOLEIL]
Battin-Leclerc, Frédérique [Auteur]
Laboratoire Réactions et Génie des Procédés [LRGP]
Hochlaf, Majdi [Auteur]
Laboratoire Instrumentation, Simulation et Informatique Scientifique [COSYS-LISIS]

Journal title :

Physical Chemistry Chemical Physics

Abbreviated title :

Phys. Chem. Chem. Phys.

Volume number :

24

Pages :

10826-10837

Publisher :

Royal Society of Chemistry (RSC)

Publication date :

2022-04-14

ISSN :

1463-9076

HAL domain(s) :

Sciences de l'ingénieur [physics]
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]

English abstract : [en]

tert-Butyl hydroperoxide (tBuOOH) is a common intermediate in the oxidation of organic compounds that needs to be accurately quantified in complex gas mixtures for the development of chemical kinetic models of low temperature ...
Show more >tert-Butyl hydroperoxide (tBuOOH) is a common intermediate in the oxidation of organic compounds that needs to be accurately quantified in complex gas mixtures for the development of chemical kinetic models of low temperature combustion. This work presents a combined theoretical and experimental investigation on the synchrotron-based VUV single photon ionization of gas-phase tBuOOH in the 9.0 - 11.0 eV energy range, including dissociative ionization processes. Computations consist of the determination of the structures, vibrational frequencies and the energetics of neutral and ionic tBuOOH. The Franck–Condon spectrum for the tBuOOH+ (X+) + e− ← tBuOOH (X) + hν transition is computed, where special treatment is undertaken because of the flexibility of tBuOOH, in particular regarding the OOH group. Through comparison of the experimental mass-selected threshold photoelectron spectra with explicitly correlated coupled cluster calculations and Franck–Condon simulations that account for the flexibility of the molecule, an estimation of the ionization energy is given. The appearance energy of the only fragment observed within the above-mentioned energy range, identified as the tert-butyl C4H9+, is also reported. Finally, the signal branching ratio between the parent and the fragment ions is provided as a function of photon energy, essential to quantify tBuOOH in gas-phase oxidation/combustion experiments via advanced mass spectrometry techniques.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

Administrative institution(s) :

Université de Lille
CNRS

Collections :

• Physicochimie des Processus de Combustion et de l'Atmosphère (PC2A) - UMR 8522

Research team(s) :

PhysicoChimie de la Combustion (PC2)

Submission date :

2022-10-23T10:45:23Z
2022-10-24T10:08:38Z