Deutsch
 
Benutzerhandbuch Datenschutzhinweis Impressum Kontakt
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT

Freigegeben

Zeitschriftenartikel

Photochemistry of methyl hypobromite (CH3OBr): excited states and photoabsorption spectrum

MPG-Autoren
/persons/resource/persons188385

Stojanović,  Ljiljana
Research Group Barbatti, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

/persons/resource/persons139980

Pereira Rodrigues,  Gessenildo
Research Group Barbatti, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Universidade Federal da Paraiba;

/persons/resource/persons58410

Barbatti,  Mario
Research Group Barbatti, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Aix Marseille Université, CNRS, ICR UMR7273 ;

Externe Ressourcen
Es sind keine Externen Ressourcen verfügbar
Volltexte (frei zugänglich)
Es sind keine frei zugänglichen Volltexte verfügbar
Ergänzendes Material (frei zugänglich)

c5ra18578e1.pdf
(Ergänzendes Material), 599KB

Zitation

Stojanović, L., Pereira Rodrigues, G., Aziz, S. G., Hilal, R. H., & Barbatti, M. (2015). Photochemistry of methyl hypobromite (CH3OBr): excited states and photoabsorption spectrum. RSC Advances, 5, 97003-97015. doi:10.1039/C5RA18578E.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0029-6432-B
Zusammenfassung
The singlet and triplet excited states of CH3OBr with excitation energies up to ∼9.5 eV are studied using the multi-reference configuration interaction with singles and doubles method (MRCI-SD) and several single-reference methods, including time-dependent density functional theory (TD-DFT), coupled-cluster (linear-response CC2 and equation-of-motion CCSD and CCSD(T)), and algebraic diagrammatic construction (ADC(2)). Among the single-reference methods, coupled-cluster gives vertical excitation energies and oscillator strengths comparable to the MRCI-SD values for the majority of excited states. The absorption cross section in the gas phase in the region between 2 and 8.5 eV was simulated with CCSD using the nuclear ensemble approach. The computed spectrum predicts two intense absorption bands. The first band, peaked at ∼7.0 eV, is induced by Rydberg excitation. The second band has a strong overlap between a broad σσ* transition and three Rydberg transitions, resulting in two peaks at 7.7 and 7.9 eV. The spectrum also features a low-intensity band peaking at ∼4.6 eV due to nσ* excitation. The intensity of this band is influenced by spin–orbit coupling effects. We analyzed the dissociation pathways along the O–Br and C–O coordinates by computing rigid potential energy curves of the ground and the lowest-lying singlet and triplet excited states, and discussed the possible dissociation products. Due to the specific electronic structure of the excited states, characterized by multireference, double excitations, and Rydberg states occurring in the low-energy region, their correct description along dissociation coordinates is feasible only with MRCI-SD.