Soft X-ray Chlorine Photolysis on Chlorobenzene Ice: An Experimental and Theoretical Study.
J Phys Chem A
; 123(7): 1389-1398, 2019 Feb 21.
Article
em En
| MEDLINE
| ID: mdl-30673243
An experimental and theoretical study of the photoinduced homolysis of the carbon-chlorine bond in an ice matrix of chlorobenzene is presented. A condensed chlorobenzene film has been grown in situ and near edge X-ray fine structure (NEXAFS) spectra were collected after exposing the condensed film to a monochromatic photon beam centered at the 2822 eV resonant excitation of chlorine and at 2850 eV. The photoabsorption to the Cl 1s â σ* and Cl 1s â π* states has been measured and the hypothesis of free radical coupling reactions was investigated via time-dependent density functional theory (TD-DFT) and complete active space self-consistent field (CASSCF) calculations. Also, potential energy pathways to the C-Cl cleavage have been obtained at the CASSCF level to the Cl 1s â σ*, 1s â π*, and 1s â ∞ states. A strong dissociative character was only found for the Cl 1s â σ* resonance.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Brasil
País de publicação:
Estados Unidos