open access publication

Article, 2024

Understanding X-ray absorption in liquid water using triple excitations in multilevel coupled cluster theory

Nature Communications, ISSN 2041-1723, Volume 15, 1, Page 3551, 10.1038/s41467-024-47690-x

Contributors

Folkestad, Sarai Dery 0000-0002-8569-4886 [1] Paul, Alexander Christian 0000-0002-7547-445X [1] Paul (Née Matveeva), Regina [1] Coriani, Sonia 0000-0002-4487-897X [2] Odelius, Michael 0000-0002-7023-2486 [3] Iannuzzi, Marcella [4] Koch, Henrik 0000-0002-8367-8727 (Corresponding author) [1]

Affiliations

  1. [1] Norwegian University of Science and Technology
    2. [NORA names: Norway; Europe, Non-EU; Nordic; OECD];
  2. [2] Technical University of Denmark
    3. [NORA names: DTU Technical University of Denmark; University; Denmark; Europe, EU; Nordic; OECD];
  3. [3] Stockholm University
    4. [NORA names: Sweden; Europe, EU; Nordic; OECD];
  4. [4] University of Zurich
    5. [NORA names: Switzerland; Europe, Non-EU; OECD]

Abstract

X-ray absorption (XA) spectroscopy is an essential experimental tool to investigate the local structure of liquid water. Interpretation of the experiment poses a significant challenge and requires a quantitative theoretical description. High-quality theoretical XA spectra require reliable molecular dynamics simulations and accurate electronic structure calculations. Here, we present the first successful application of coupled cluster theory to model the XA spectrum of liquid water. We overcome the computational limitations on system size by employing a multilevel coupled cluster framework for large molecular systems. Excellent agreement with the experimental spectrum is achieved by including triple excitations in the wave function and using molecular structures from state-of-the-art path-integral molecular dynamics. We demonstrate that an accurate description of the electronic structure within the first solvation shell is sufficient to successfully model the XA spectrum of liquid water within the multilevel framework. Furthermore, we present a rigorous charge transfer analysis of the XA spectrum, which is reliable due to the accuracy and robustness of the electronic structure methodology. This analysis aligns with previous studies regarding the character of the prominent features of the XA spectrum of liquid water.

Keywords

X-ray, X-ray absorption, XA spectra, absorption, accuracy, accurate description, accurate electronic structure calculations, agreement, analysis, calculations, charge, charge transfer analysis, cluster theory, clustering framework, computational limitations, coupled cluster theory, description, dynamics, dynamics simulations, electronic structure, electronic structure calculations, electronic structure methodology, excellent agreement, excitation, experimental spectra, experimental tool, experiments, features, framework, function, interpretation, limitations, liquid water, local structure, local structure of liquid water, methodology, molecular dynamics, molecular dynamics simulations, molecular structure, molecular systems, multilevel framework, path integral molecular dynamics, quantitative theoretical description, robustness, shell, simulation, size, solvation, solvation shell, spectra, spectrum of liquid water, structure, structure calculations, structure of liquid water, structured methodology, study, system, system size, theoretical description, theory, tools, transfer analysis, triple excitations, water, wave, wave functions

Funders

  • European Research Council
  • Swedish Research Council
  • The Research Council of Norway
  • European Commission

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