RIXS within the coupled-cluster framework reveals the hidden transitions of transient species in ionized liquid water

ORAL

Abstract

X-ray spectroscopies such as resonant inelastic X-ray scattering (RIXS) expand our ability to investigate the chemical structure and dynamics; in particular, when augmented with reliable theoretical tools. Computing the RIXS spectra, however, is challenging; primarily due to the difficulties in computing the underlying core-excited virtual states that are embedded inside the valence-ionization continuum in a converged fashion. We will present a novel electronic structure method within the equation-of-motion coupled cluster framework that facilitates converged calculations of the RIXS spectra for both closed- and open-shell species. We will illustrate the capabilities of our approach by measuring its performance in modeling the RIXS spectrum of the transient aqueous OH radical formed in ionized liquid water against experiments. We will provide orbital characterization of the distinct peaks in the RIXS spectrum of the OH radical for absorption below water’s absorption edge. We will provide ab initio explanation of why the intermolecular charge-transfer transitions of aqueous OH radical, that are dominant in UV-visible spectrum, are suppressed in RIXS revealing the hidden localized valence transition.

*This work was supported by the U.S. National Science Foundation (No. CHE-1856342).

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Presenters

  • Kaushik Nanda

    • Department of Chemistry, University of Southern California, USA

Authors

  • Kaushik Nanda

    • Department of Chemistry, University of Southern California, USA

  • Ludvig Kjellsson

    • Department of Physics and Astronomy, Uppsala University, Sweden

  • Jan-Erik Rubensson

    • Department of Physics and Astronomy, Uppsala University, Sweden

  • Gilles Doumy

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Stephen Southworth

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Phay J Ho

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Anne M March

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Andre Al Haddad

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Yoshiaki Kumagai

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Ming-Feng Tu

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA

  • Muhammad Shafiq Mohd Yusof

    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore

  • Tushar Debnath

    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore

  • Caroline Arnold

    • Center for Free-Electron Laser Science, DESY, Germany

  • Ralph Welsch

    • Center for Free-Electron Laser Science, DESY, Germany

  • Ludger Inhester

    • Center for Free-Electron Laser Science, DESY, Germany

  • Robin Santra

    • Center for Free-Electron Laser Science, DESY, Germany

  • Marc Simon

    • Sorbonne Université and CNRS, Laboratoire de Chimie Physique-Matière et Rayonnement, France

  • William F Schlotter

    • LCLS, SLAC National Accelerator Laboratory, USA

  • Stefan Moeller

    • LCLS, SLAC National Accelerator Laboratory, USA

  • Giacomo Coslovich

    • LCLS, SLAC National Accelerator Laboratory, USA

  • Jake Korelek

    • LCLS, SLAC National Accelerator Laboratory, USA
    • SLAC National Accelerator Laboratory

  • Daniel DePonte

    • LCLS, SLAC National Accelerator Laboratory, USA

  • Zhi-Heng Loh

    • Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore

  • Anna Krylov

    • Univ of Southern California
    • Department of Chemistry, University of Southern California, USA

  • Linda Young

    • Chemical Sciences and Engineering Division, Argonne National Laboratory, USA