Electronic state spectroscopy of C2Cl4

The VUV spectrum of C2Cl4 is reported in the energy range 3.8-10.8 eV (325-115 nm). Several photoabsorption features are observed for the first time, including a very weak low-lying band which is provisionally attributed to a pi -> pi* triplet transition. Recent ab initio calculations of the molecule's electronic transitions [S. Arulmozhiraja, M. Ehara, H. Nakatsuji, J. Chem. Phys. 129 (2008) 174506] provide the basis for the present assignments below 8.5 eV. An extended nd pi series is proposed to account for several higher-energy Rydberg bands. The identification of vibrational structure, dominated by symmetric C=C and CCl2 stretching in excitations from the HOMO, largely agrees with previous spectroscopic studies. The present absolute photoabsorption cross sections cover a wider energy range than the previous measurements and are used to calculate UV photolysis lifetimes of this aeronomic molecule at altitudes between 20 and 50 km. (C) 2009 Elsevier B. V. All rights reserved.