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Quantum Mechanical Versus Polarizable Embedding Schemes: A Study of the Xray Absorption Spectra of Aqueous Ammonia and Ammonium
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Number of Authors: 72024 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 20, no 10, p. 4161-4169Article in journal (Refereed) Published
Abstract [en]

The X-ray absorption spectra of aqueous ammonia and ammonium are computed using a combination of coupled cluster singles and doubles (CCSD) with different quantum mechanical and molecular mechanical embedding schemes. Specifically, we compare frozen Hartree–Fock (HF) density embedding, polarizable embedding (PE), and polarizable density embedding (PDE). Integrating CCSD with frozen HF density embedding is possible within the CC-in-HF framework, which circumvents the conventional system-size limitations of standard coupled cluster methods. We reveal similarities between PDE and frozen HF density descriptions, while PE spectra differ significantly. By including approximate triple excitations, we also investigate the effect of improving the electronic structure theory. The spectra computed using this approach show an improved intensity ratio compared to CCSD-in-HF. Charge transfer analysis of the excitations shows the local character of the pre-edge and main-edge, while the post-edge is formed by excitations delocalized over the first solvation shell and beyond.

Place, publisher, year, edition, pages
2024. Vol. 20, no 10, p. 4161-4169
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Theoretical Chemistry
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URN: urn:nbn:se:su:diva-232390DOI: 10.1021/acs.jctc.4c00105ISI: 001224816600001PubMedID: 38713524Scopus ID: 2-s2.0-85193258753OAI: oai:DiVA.org:su-232390DiVA, id: diva2:1889858
Available from: 2024-08-16 Created: 2024-08-16 Last updated: 2024-08-16Bibliographically approved

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Odelius, Michael

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