The electronic excited states of dichloromethane ...
Document type :
Compte-rendu et recension critique d'ouvrage
Title :
The electronic excited states of dichloromethane in the 5.8-10.8 eV energy range investigated by experimental and theoretical methods
Author(s) :
Lange, E. [Auteur]
Jones, N.C. [Auteur]
Centre for Storage Ring Facilities [Aarhus] [ISA]
Hoffmann, S.V. [Auteur]
Centre for Storage Ring Facilities [Aarhus] [ISA]
Lozano, A.I. [Auteur]
Kumar, S. [Auteur]
Homem, M.G.P. [Auteur]
Universidade Federal de São Carlos [São Carlos] [UFSCar]
Śmiałek, M.A. [Auteur]
Duflot, D. [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Brunger, M.J. [Auteur]
Limão-Vieira, P. [Auteur]
Jones, N.C. [Auteur]
Centre for Storage Ring Facilities [Aarhus] [ISA]
Hoffmann, S.V. [Auteur]
Centre for Storage Ring Facilities [Aarhus] [ISA]
Lozano, A.I. [Auteur]
Kumar, S. [Auteur]
Homem, M.G.P. [Auteur]
Universidade Federal de São Carlos [São Carlos] [UFSCar]
Śmiałek, M.A. [Auteur]
Duflot, D. [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Brunger, M.J. [Auteur]
Limão-Vieira, P. [Auteur]
Journal title :
Journal of Quantitative Spectroscopy and Radiative Transfer
Pages :
107172
Publisher :
Elsevier
Publication date :
2020-06-17
ISSN :
0022-4073
HAL domain(s) :
Chimie/Chimie théorique et/ou physique
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
Physique [physics]/Physique [physics]/Chimie-Physique [physics.chem-ph]
English abstract : [en]
We present a comprehensive experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectrum of dichloromethane, CH<sub>2</sub>Cl<sub>2</sub>, with absolute cross sections determined for the full 5.8–10.8 eV ...
Show more >We present a comprehensive experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectrum of dichloromethane, CH<sub>2</sub>Cl<sub>2</sub>, with absolute cross sections determined for the full 5.8–10.8 eV energy-range. The calculations on the vertical excitation energies and oscillator strengths were performed using the equation-of-motion coupled cluster method, restricted to the single and double excitations level (EOM-CCSD), and were used to help analyse the valence and Rydberg structures in the photoabsorption spectrum. The present spectrum additionally reveals several new features not previously reported in the literature, with particular reference to the valence σ*<sub>CCl</sub> (10a<sub>1</sub>) ← n<sub>Cl</sub> (7b<sub>2</sub>) (1<sup>1</sup><i>B<sub>2</sub></i> ← X<sup>1</sup><i>A<sub>1</sub></i>) and (σ*<sub>CCl</sub> (10a<sub>1</sub>) ← n<sub>Cl</sub> (9a<sub>1</sub>) + σ*<sub>CH</sub> (11a<sub>1</sub>) ← n<sub>Cl</sub> (7b<sub>2</sub>)) (1<sup>1</sup><i>A<sub>1</sub></i> ← X <sup>1</sup><i>A<sub>1</sub></i>) transitions at 7.519 and 7.793 eV. A vibrational progression of the CCl<sub>2</sub> symmetric stretching, ν'<sub>3</sub>, and CCl<sub>2</sub> scissoring, ν'<sub>4</sub> (a<sub>1</sub>), modes have also been assigned for the first time in the 7.4–8.6 eV energy range. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of dichloromethane in the Earth's atmosphere (0–50 km). Potential energy curves as a function of the C–Cl coordinate, for the four lowest-lying excited A′ and A″ electronic states, have additionally been calculated at the EOM-CCSD level of theory.Show less >
Show more >We present a comprehensive experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectrum of dichloromethane, CH<sub>2</sub>Cl<sub>2</sub>, with absolute cross sections determined for the full 5.8–10.8 eV energy-range. The calculations on the vertical excitation energies and oscillator strengths were performed using the equation-of-motion coupled cluster method, restricted to the single and double excitations level (EOM-CCSD), and were used to help analyse the valence and Rydberg structures in the photoabsorption spectrum. The present spectrum additionally reveals several new features not previously reported in the literature, with particular reference to the valence σ*<sub>CCl</sub> (10a<sub>1</sub>) ← n<sub>Cl</sub> (7b<sub>2</sub>) (1<sup>1</sup><i>B<sub>2</sub></i> ← X<sup>1</sup><i>A<sub>1</sub></i>) and (σ*<sub>CCl</sub> (10a<sub>1</sub>) ← n<sub>Cl</sub> (9a<sub>1</sub>) + σ*<sub>CH</sub> (11a<sub>1</sub>) ← n<sub>Cl</sub> (7b<sub>2</sub>)) (1<sup>1</sup><i>A<sub>1</sub></i> ← X <sup>1</sup><i>A<sub>1</sub></i>) transitions at 7.519 and 7.793 eV. A vibrational progression of the CCl<sub>2</sub> symmetric stretching, ν'<sub>3</sub>, and CCl<sub>2</sub> scissoring, ν'<sub>4</sub> (a<sub>1</sub>), modes have also been assigned for the first time in the 7.4–8.6 eV energy range. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of dichloromethane in the Earth's atmosphere (0–50 km). Potential energy curves as a function of the C–Cl coordinate, for the four lowest-lying excited A′ and A″ electronic states, have additionally been calculated at the EOM-CCSD level of theory.Show less >
Language :
Anglais
Popular science :
Non
ANR Project :
Source :
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