title: The influence of the bromine atom Cooper minimum on the photoelectron angular distributions and branching ratios of the four outermost bands of bromobenzene.
abstract: Angle resolved photoelectron spectra of the X̃(2)B1, Ã(2)A2, B̃(2)B2, and C̃(2)B1 states of bromobenzene have been recorded over the excitation range 20.5-94 eV using linearly polarized synchrotron radiation. The photoelectron anisotropy parameters and electronic branching ratios derived from these spectra have been compared to theoretical predictions obtained with the continuum multiple scattering approach. This comparison shows that ionization from the 8b2 orbital and, to a lesser extent, the 4b1 orbital is influenced by the Cooper minimum associated with the bromine atom. The 8b2 and 4b1 orbitals are nominally bromine lone-pairs, but the latter orbital interacts strongly with the π-orbitals in the benzene ring and this leads to a reduced atomic character. Simulations of the X̃(2)B1, B̃(2)B2, and C̃(2)B1 state photoelectron bands have enabled most of the vibrational structures appearing in the experimental spectra to be assigned. Many of the photoelectron peaks exhibit an asymmetric shape with a tail towards low binding energy. This asymmetry has been examined in the simulations of the vibrationally unexcited peak, due mainly to the adiabatic transition, in the X̃(2)B1 state photoelectron band. The simulations show that the asymmetric profile arises from hot-band transitions. The inclusion of transitions originating from thermally populated levels results in a satisfactory agreement between the experimental and simulated peak shapes.
authors.affiliation: School of Chemistry, University of Nottingham, Nottingham NG7 2RD, United Kingdom.
authors.forename: I
authors.initials: I
authors.lastname: Powis
authors.affiliation: Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD, United Kingdom.
authors.forename: D M P
authors.initials: DM
authors.lastname: Holland
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France.
authors.forename: E
authors.initials: E
authors.lastname: Antonsson
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France.
authors.forename: M
authors.initials: M
authors.lastname: Patanen
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France.
authors.forename: C
authors.initials: C
authors.lastname: Nicolas
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France.
authors.forename: C
authors.initials: C
authors.lastname: Miron
authors.affiliation: Interdisciplinary Centre for Scientific Computation, University of Heidelberg, Im Neuenheimer Feld 368, D-69120 Heidelberg, Germany.
authors.forename: M
authors.initials: M
authors.lastname: Schneider
authors.affiliation: Favorsky's Institute of Chemistry, SB RAS, 664033 Irkutsk, Russia.
authors.forename: D Yu
authors.initials: DY
authors.lastname: Soshnikov
authors.affiliation: Interdisciplinary Centre for Scientific Computation, University of Heidelberg, Im Neuenheimer Feld 368, D-69120 Heidelberg, Germany.
authors.forename: A
authors.initials: A
authors.lastname: Dreuw
authors.affiliation: Favorsky's Institute of Chemistry, SB RAS, 664033 Irkutsk, Russia.
authors.forename: A B
authors.initials: AB
authors.lastname: Trofimov