title: Core excitations of naphthalene: vibrational structure versus chemical shifts.
abstract: High-resolution x-ray photoelectron emission (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectra of naphthalene are analyzed in terms of the initial state chemical shifts and the vibrational fine structure of the excitations. Carbon atoms located at peripheral sites experience only a small chemical shift and exhibit rather similar charge-vibrational coupling, while the atoms in the bridging positions differ substantially. In the XPS spectra, C-H stretching modes provide important contributions to the overall shape of the spectrum. In contrast, the NEXAFS spectrum contains only vibrational progressions from particular C-C stretching modes. The accuracy of ab initio calculations of absolute electronic transition energies is discussed in the context of minute chemical shifts, the vibrational fine structure, and the state multiplicity.
authors.affiliation: Royal Institute of Technology, S-106 91 Stockholm, Sweden.
authors.forename: I
authors.initials: I
authors.lastname: Minkov
authors.forename: F
authors.initials: F
authors.lastname: Gel'mukhanov
authors.forename: R
authors.initials: R
authors.lastname: Friedlein
authors.forename: W
authors.initials: W
authors.lastname: Osikowicz
authors.forename: C
authors.initials: C
authors.lastname: Suess
authors.forename: G
authors.initials: G
authors.lastname: Ohrwall
authors.forename: S L
authors.initials: SL
authors.lastname: Sorensen
authors.forename: S
authors.initials: S
authors.lastname: Braun
authors.forename: R
authors.initials: R
authors.lastname: Murdey
authors.forename: W R
authors.initials: WR
authors.lastname: Salaneck
authors.forename: H
authors.initials: H
authors.lastname: Agren