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The electronic excited states of dichloromethane in the 5.8-10.8 eV energy range investigated by experimental and theoretical methods

Abstract

We present a comprehensive experimental high-resolution vacuum ultraviolet (VUV) photoabsorption spectrum of dichloromethane, CH 2 Cl 2 , 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 photoab- sorption spectrum. The present spectrum additionally reveals several new features not previously re- ported in the literature, with particular reference to the valence σ∗C C l ( 10 a 1 ) ← n Cl ( 7 b 2 ) ( 1 1 B 2 ← ̃ X 1 A 1 ) and ( σ∗C C l ( 10 a 1 ) ← n Cl ( 9 a 1 ) + σ∗CH ( 11 a 1 ) ← n Cl ( 7 b 2 ) ) ( 1 1 A 1 ← ̃ X 1 A 1 ) transitions at 7.519 and 7.793 eV. A vibrational progression of the CCl 2 symmetric stretching, ν′ 3 , and CCl 2 scissoring, v ′ 4 ( a 1 ) , 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 atmo- sphere (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.

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DOI:
Digital Object Identifier (open in new tab) 10.1016/j.jqsrt.2020.107172
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Category:
Articles
Type:
artykuły w czasopismach
Published in:
JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER no. 253,
ISSN: 0022-4073
Language:
English
Publication year:
2020
Bibliographic description:
Lange E., Jones N., Hoffmann S., Lozano A., Kumar S., Homem M., Śmiałek-Telega M., Duflot D., Brunger M., Limão-Vieira P.: The electronic excited states of dichloromethane in the 5.8-10.8 eV energy range investigated by experimental and theoretical methods// JOURNAL OF QUANTITATIVE SPECTROSCOPY & RADIATIVE TRANSFER -Vol. 253, (2020), s.107172-
DOI:
Digital Object Identifier (open in new tab) 10.1016/j.jqsrt.2020.107172
Verified by:
Gdańsk University of Technology

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