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Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters.
J Chem Theory Comput. 2019 Sep 10; 15(9):4816-4833.JC

Abstract

The importance of many-body effects in the hydration of the hydronium ion (H3O+) is investigated through a systematic analysis of the many-body expansion of the interaction energy carried out at the coupled-cluster level of theory for the low-lying isomers of H3O+(H2O)n clusters with n = 1-5. This is accomplished by partitioning individual fragments extracted from the whole clusters into "groups" that are classified by both the number of H3O+ and water molecules and the hydrogen-bonding connectivity within a given fragment. Effects due to the presence of the Zundel ion, (H5O2)+, are analyzed by further partitioning fragment groups by the "context" of their parent clusters. With the aid of the absolutely localized molecular orbital energy decomposition analysis (ALMO EDA), this structure-based partitioning is found to largely correlate with the character of different many-body interactions, such as cooperative and anticooperative hydrogen bonding, within each fragment. This analysis emphasizes the importance of a many-body representation of inductive electrostatics and charge transfer in modeling the hydration of an excess proton in water. The comparison between the reference coupled-cluster many-body interaction terms with the corresponding values obtained with various exchange-correlation functionals demonstrates that many of these functionals yield an unbalanced treatment of the H3O+(H2O)n configuration space.

Authors+Show Affiliations

Department of Chemistry and Biochemistry , University of California San Diego , La Jolla , California 92093 , United States.Department of Chemistry and Biochemistry , University of California San Diego , La Jolla , California 92093 , United States. Materials Science and Engineering , University of California San Diego , La Jolla , California 92093 , United States. San Diego Supercomputer Center , University of California San Diego , La Jolla , California 92093 , United States.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31345030

Citation

Egan, Colin K., and Francesco Paesani. "Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters." Journal of Chemical Theory and Computation, vol. 15, no. 9, 2019, pp. 4816-4833.
Egan CK, Paesani F. Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters. J Chem Theory Comput. 2019;15(9):4816-4833.
Egan, C. K., & Paesani, F. (2019). Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters. Journal of Chemical Theory and Computation, 15(9), 4816-4833. https://doi.org/10.1021/acs.jctc.9b00418
Egan CK, Paesani F. Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters. J Chem Theory Comput. 2019 Sep 10;15(9):4816-4833. PubMed PMID: 31345030.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Assessing Many-Body Effects of Water Self-Ions. II: H3O+(H2O)n Clusters. AU - Egan,Colin K, AU - Paesani,Francesco, Y1 - 2019/08/15/ PY - 2019/7/28/pubmed PY - 2019/7/28/medline PY - 2019/7/27/entrez SP - 4816 EP - 4833 JF - Journal of chemical theory and computation JO - J Chem Theory Comput VL - 15 IS - 9 N2 - The importance of many-body effects in the hydration of the hydronium ion (H3O+) is investigated through a systematic analysis of the many-body expansion of the interaction energy carried out at the coupled-cluster level of theory for the low-lying isomers of H3O+(H2O)n clusters with n = 1-5. This is accomplished by partitioning individual fragments extracted from the whole clusters into "groups" that are classified by both the number of H3O+ and water molecules and the hydrogen-bonding connectivity within a given fragment. Effects due to the presence of the Zundel ion, (H5O2)+, are analyzed by further partitioning fragment groups by the "context" of their parent clusters. With the aid of the absolutely localized molecular orbital energy decomposition analysis (ALMO EDA), this structure-based partitioning is found to largely correlate with the character of different many-body interactions, such as cooperative and anticooperative hydrogen bonding, within each fragment. This analysis emphasizes the importance of a many-body representation of inductive electrostatics and charge transfer in modeling the hydration of an excess proton in water. The comparison between the reference coupled-cluster many-body interaction terms with the corresponding values obtained with various exchange-correlation functionals demonstrates that many of these functionals yield an unbalanced treatment of the H3O+(H2O)n configuration space. SN - 1549-9626 UR - https://www.unboundmedicine.com/medline/citation/31345030/Assessing_Many-Body_Effects_of_Water_Self-Ions._II:_H3O+(H2O)n_Clusters DB - PRIME DP - Unbound Medicine ER -
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