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Radicals in aqueous solution: assessment of density-corrected SCAN functional


Belleflamme, Fabian; Hutter, Jürg (2023). Radicals in aqueous solution: assessment of density-corrected SCAN functional. Physical Chemistry Chemical Physics (PCCP), 25(31):20817-20836.

Abstract

We study self-interaction effects in solvated and strongly-correlated cationic molecular clusters, with a focus on the solvated hydroxyl radical. To address the self-interaction issue, we apply the DC-r2SCAN method, with the auxiliary density matrix approach. Validating our method through simulations of bulk liquid water, we demonstrate that DC-r2SCAN maintains the structural accuracy of r2SCAN while effectively addressing spin density localization issues. Extending our analysis to solvated cationic molecular clusters, we find that the hemibonded motif in the [CH3S∴CH3SH]+ cluster is disrupted in the DC-r2SCAN simulation, in contrast to r2SCAN that preserves the (three-electron-two-center)-bonded motif. Similarly, for the [SH∴SH2]+ cluster, r2SCAN restores the hemibonded motif through spin leakage, while DC-r2SCAN predicts a weaker hemibond formation influenced by solvent-solute interactions. Our findings demonstrate the potential of DC-r2SCAN combined with the auxiliary density matrix method to improve electronic structure calculations, providing insights into the properties of solvated cationic molecular clusters. This work contributes to the advancement of self-interaction corrected electronic structure theory and offers a computational framework for modeling condensed phase systems with intricate correlation effects.

Abstract

We study self-interaction effects in solvated and strongly-correlated cationic molecular clusters, with a focus on the solvated hydroxyl radical. To address the self-interaction issue, we apply the DC-r2SCAN method, with the auxiliary density matrix approach. Validating our method through simulations of bulk liquid water, we demonstrate that DC-r2SCAN maintains the structural accuracy of r2SCAN while effectively addressing spin density localization issues. Extending our analysis to solvated cationic molecular clusters, we find that the hemibonded motif in the [CH3S∴CH3SH]+ cluster is disrupted in the DC-r2SCAN simulation, in contrast to r2SCAN that preserves the (three-electron-two-center)-bonded motif. Similarly, for the [SH∴SH2]+ cluster, r2SCAN restores the hemibonded motif through spin leakage, while DC-r2SCAN predicts a weaker hemibond formation influenced by solvent-solute interactions. Our findings demonstrate the potential of DC-r2SCAN combined with the auxiliary density matrix method to improve electronic structure calculations, providing insights into the properties of solvated cationic molecular clusters. This work contributes to the advancement of self-interaction corrected electronic structure theory and offers a computational framework for modeling condensed phase systems with intricate correlation effects.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Physics and Astronomy
Physical Sciences > Physical and Theoretical Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, General Physics and Astronomy
Language:English
Date:1 January 2023
Deposited On:15 Dec 2023 11:53
Last Modified:29 Jun 2024 01:38
Publisher:Royal Society of Chemistry
ISSN:1463-9076
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1039/d3cp02517a
PubMed ID:37497572
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution 4.0 International (CC BY 4.0)