The valence shell electronic states of ethylene sulphide studied by photoabsorption and ab initio multireference configuration interaction calculations

• Published in: Chemical physics Vol. 344; no. 3; pp. 227 - 236
• Main Authors: Holland, D.M.P., Shaw, D.A., Walker, I.C., McEwen, I.J., Guest, M.F.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 13.03.2008
• Subjects: Ab initio multireference configuration interaction calculations; Photoabsorption; Rydberg and valence states; Ab initio multireference configuration interaction calculations; Photoabsorption; Rydberg and valence states
• ISSN: 0301-0104
• DOI: 10.1016/j.chemphys.2008.01.006

The absolute photoabsorption cross section of ethylene sulphide has been measured between threshold and 30 eV using monochromated synchrotron radiation. Below the ionisation threshold the spectrum exhibits numerous sharp peaks associated with Rydberg states belonging to series converging onto the X ∼ 2 B 1 limit. At excitation energies above the ionisation threshold at 9 eV intravalence transitions play a dominant role, resulting in the appearance of prominent broad bands. Much weaker structure ascribed to Rydberg states associated with excitation from the 4b 2, 8a 1 or 2b 1 orbitals is also discernible. Ab initio multireference configuration interaction calculations have been performed to obtain excitation energies for valence electron transitions into Rydberg or virtual valence orbitals. These theoretical predictions have enabled assignments to be proposed for most of the structure due to Rydberg series converging onto the X ∼ 2 B 1 limit. The calculations show that configuration interaction is important in the description of many of the excited states.