title: Site-selective photoemission from delocalized valence shells induced by molecular rotation.
abstract: Due to the generally delocalized nature of molecular valence orbitals, valence-shell spectroscopies do not usually allow to specifically target a selected atom in a molecule. However, in X-ray electron spectroscopy, the photoelectron momentum is large and the recoil angular momentum transferred to the molecule is larger when the photoelectron is ejected from a light atom compared with a heavy one. This confers an extreme sensitivity of the rotational excitation to the ionization site. Here we show that, indeed, the use of high-energy photons to photoionize valence-shell electrons of hydrogen chloride offers an unexpected way to decrypt the atomic composition of the molecular orbitals due to the rotational dependence of the photoionization profiles. The analysis of the site-specific rotational envelopes allows us to disentangle the effects of the two main mechanisms of rotational excitation, based on angular momentum exchange between the molecule and either the incoming photon or the emitted electron.
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France.
authors.forename: Catalin
authors.initials: C
authors.lastname: Miron
authors.affiliation: 1] Theoretical Chemistry and Biology, School of Biotechnology, KTH, Royal Institute of Technology, S-106 91 Stockholm, Sweden [2].
authors.forename: Quan
authors.initials: Q
authors.lastname: Miao
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Nicolas
authors.affiliation: SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA.
authors.forename: John D
authors.initials: JD
authors.lastname: Bozek
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France.
authors.forename: Witold
authors.initials: W
authors.lastname: Andrałojć
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France.
authors.forename: Minna
authors.initials: M
authors.lastname: Patanen
authors.affiliation: 1] Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France [2] Instituto de Química, Universidade Federal do Rio de Janeiro, Ilha do Fundão, Rio de Janeiro, Rio de Janeiro 2194 9900, Brazil.
authors.forename: Grazieli
authors.initials: G
authors.lastname: Simões
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France.
authors.forename: Oksana
authors.initials: O
authors.lastname: Travnikova
authors.affiliation: Theoretical Chemistry and Biology, School of Biotechnology, KTH, Royal Institute of Technology, S-106 91 Stockholm, Sweden.
authors.forename: Hans
authors.initials: H
authors.lastname: Ågren
authors.affiliation: 1] Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette, France [2] Theoretical Chemistry and Biology, School of Biotechnology, KTH, Royal Institute of Technology, S-106 91 Stockholm, Sweden.
authors.forename: Faris
authors.initials: F
authors.lastname: Gel'mukhanov