title: Matrix effects in the carbon 1s near edge x-ray absorption fine structure spectra of condensed alkanes.
abstract: The carbon 1s near edge x-ray absorption fine structure (NEXAFS) spectra of simple gaseous alkane molecules differ from the spectra of the same alkane molecules in the condensed phase. The origin of these large, systematic differences is poorly understood. The NEXAFS spectra of gaseous alkanes are interpreted as a progression of core-->Rydberg transitions with distinctive vibronic structure. The interpretation of the NEXAFS spectra of condensed phase alkanes is varied. Specifically, the degree of Rydberg character in the pre-edge core excited states of condensed alkanes is controversial. We determined the character of core excited states in condensed alkanes with a combination of experiment and computational study. From this, we have determined the nature of matrix effects for these species. The high-resolution carbon 1s NEXAFS spectrum of gaseous neopentane is dramatically different from its condensed phase spectrum, a striking illustration of the dramatic spectroscopic changes that occur upon condensation. High quality ab initio calculations of a cluster designed to model the solid phase environment provide definitive evidence for the reduction of Rydberg character and support the assignment of sigma*C-H) valence character in the pre-edge features in the NEXAFS spectra of condensed alkanes.
authors.affiliation: Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, SK S7N 5C9, Canada. stephen.urquhart@usask.ca
authors.forename: Stephen G
authors.initials: SG
authors.lastname: Urquhart
authors.forename: Rob
authors.initials: R
authors.lastname: Gillies