Photodissociation of ethylene sulfide at 193 nm: a photofragment translational spectroscopy study with VUV synchrotron radiation and ab initio calculations

F Qi; O Sorkhabi; A G Suits; S H Chien; W K Li

doi:10.1021/ja003314v

Photodissociation of ethylene sulfide at 193 nm: a photofragment translational spectroscopy study with VUV synchrotron radiation and ab initio calculations

J Am Chem Soc. 2001 Jan 10;123(1):148-61. doi: 10.1021/ja003314v.

Authors

F Qi¹, O Sorkhabi, A G Suits, S H Chien, W K Li

Affiliation

¹ Chemical Sciences Division, Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. fqi@lbl.gov

PMID: 11273612
DOI: 10.1021/ja003314v

Abstract

Photodissociation of ethylene sulfide at 193 nm has been studied using photofragment translational spectroscopy and ab initio theoretical calculations. Tunable synchrotron radiation was used as a universal but selective probe of the reaction products to reveal new aspects of the photodissociation dynamics. The channel giving S + C2H4 was found to be dominated by production of ground-state sulfur atoms (S(3P):S(1D) = 1.44:1), mostly through a spin-forbidden process. The results also suggest the presence of a channel giving S(3P) in conjunction with triplet ethylene C2H4 (3B(1u)) and allow insight into the energy of the latter species near its equilibrium geometry, in which the two methylene groups occupy perpendicular planes. In addition, a channel leading to the production of H2S with C2H2 also has been observed. Our experimental results are supported and elaborated by theoretical calculations.