Orientational anisotropy due to molecular field splitting in sulfur 2p photoemission from CS2 and SF6 - theoretical treatment and application to photoelectron recoil - UTU Research Portal

A1 Refereed original research article in a scientific journal

Orientational anisotropy due to molecular field splitting in sulfur 2p photoemission from CS2 and SF6 - theoretical treatment and application to photoelectron recoil

Authors: Kukk, Edwin; Niskanen, Johannes; Travnikova, Oksana; Berholts, Marta; Kooser, Kuno; Peng, Dawei; Ismail, Iyas; Piancastelli, Maria Novella; Püttner, Ralph; Hergerhahn, Uwe; Simon, Marc

Publisher: Royal Society of Chemistry

Publication year: 2024

Journal: Physical Chemistry Chemical Physics

Journal name in source: Physical chemistry chemical physics : PCCP

Journal acronym: Phys Chem Chem Phys

Volume: 26

Issue: 32

First page : 21810

Last page: 21820

ISSN: 1463-9076

eISSN: 1463-9084

DOI: https://doi.org/10.1039/d4cp01463d

Web address : https://pubs.rsc.org/en/content/articlelanding/2024/cp/d4cp01463d

Self-archived copy’s web address: https://research.utu.fi/converis/portal/detail/Publication/457443812

Abstract

Photoelectron recoil strongly modifies the high kinetic energy photoemission spectra from atoms and molecules as well as from surface structures. In most cases studied so far, photoemission from atomic-like inner-shell or core orbitals has been assumed to be isotropic in the molecular frame of reference. However, in the presence of molecular field splitting of p or d orbitals, this assumption is not justified per se. We present a general theoretical treatment, linking the orientational distribution of gas-phase molecules to the electron emission and detection in a certain direction in the laboratory frame. The approach is then applied to the S 2p photoemission from a linear molecule such as CS₂ and we investigate, how the predicted orientational anisotropies due to molecular field splitting affect the photoelectron recoil excitations. Lastly, experimental S 2p high-kinetic-energy photoelectron spectra of SF₆ and CS₂ are analyzed using the modeled recoil lineshapes representing the anisotropy-affected recoil effects.

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Funding information in the publication:
EK acknowledges the Research Council of Finland, and MB the Estonian Research Council grant (MOBTP1013) for the financial support.