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Article: Ab initio investigation of the structure, stability, and atmospheric distribution of molecular clusters containing H2O, CO2, and N2O

TitleAb initio investigation of the structure, stability, and atmospheric distribution of molecular clusters containing H2O, CO2, and N2O
Authors
KeywordsAb initio calculations
Ab initio investigation
Bulk water
Energetic properties
Hydration energies
Issue Date2008
PublisherAmerican Geophysical Union.
Citation
Journal of Geophysical Research, 2008, v. 113 n. 19, article no. D19304 How to Cite?
AbstractWe present results from ab initio calculations for the structures and energetic properties of neutral clusters containing water, carbon dioxide, and nitrous oxide using the complete basis set CBS-Q multilevel procedure. Gas phase hydration energies ΔG0, enthalpies ΔH0, and entropies ΔS0 for the stepwise attachment of water onto clusters according to X·(H2O)n + H2O ↔ X·(H2O)n+1 (X = CO2, N 2O, and H2O) are reported for n ≤ 4. In particular, our results demonstrate that values for the incremental hydration enthalpies and entropies of all three gases CO2, N2O, and H2O asymptotically approach values characteristic of bulk water (i.e., -44.0 kJ mol-1 for the enthalpy and - 118.8 J K-1 mol-1 for the entropy of condensation) following attachment of around three to four water molecules. Our ab initio calculations indicate that water attachment onto CO2, N2O, and H2O is a thermodynamically favorable process, such that hydrated CO2·(H 2O)n, N2O(H2O)n, and H2O(H2O)n clusters would form a significant atmospheric repository of these species. Copyright 2008 by the American Geophysical Union.
Persistent Identifierhttp://hdl.handle.net/10722/58647
ISSN
2015 Impact Factor: 3.318
2015 SCImago Journal Rankings: 2.310
ISI Accession Number ID
Funding AgencyGrant Number
Swiss Federal Institute of Technology (ETH), Zurich
Schweizerischer Nationalfonds200020-113476
Funding Information:

The authors want to thank O. Suleimenov (ETH-Zurich) for valuable discussions about cluster structure optimization. We also wish to thank T. K. Ha (ETH-Zurich) for fruitful discussions on ab initio theory and its application to solving thermochemical problems. The Competence Centre for Computational Chemistry (C4) at ETH-Zurich is also thanked for providing access and support to its facilities. Finally, two anonymous reviewers and Associate Editor J. Fuentes are thanked for their constructive comments on the manuscript. This work was carried out at the Swiss Federal Institute of Technology (ETH), Zurich, and funded by Schweizerischer Nationalfonds grant 200020-113476 awarded to T. M. Seward.

References

 

DC FieldValueLanguage
dc.contributor.authorLemke, KHen_HK
dc.contributor.authorSeward, TMen_HK
dc.date.accessioned2010-05-31T03:34:20Z-
dc.date.available2010-05-31T03:34:20Z-
dc.date.issued2008en_HK
dc.identifier.citationJournal of Geophysical Research, 2008, v. 113 n. 19, article no. D19304en_HK
dc.identifier.issn0148-0227en_HK
dc.identifier.urihttp://hdl.handle.net/10722/58647-
dc.description.abstractWe present results from ab initio calculations for the structures and energetic properties of neutral clusters containing water, carbon dioxide, and nitrous oxide using the complete basis set CBS-Q multilevel procedure. Gas phase hydration energies ΔG0, enthalpies ΔH0, and entropies ΔS0 for the stepwise attachment of water onto clusters according to X·(H2O)n + H2O ↔ X·(H2O)n+1 (X = CO2, N 2O, and H2O) are reported for n ≤ 4. In particular, our results demonstrate that values for the incremental hydration enthalpies and entropies of all three gases CO2, N2O, and H2O asymptotically approach values characteristic of bulk water (i.e., -44.0 kJ mol-1 for the enthalpy and - 118.8 J K-1 mol-1 for the entropy of condensation) following attachment of around three to four water molecules. Our ab initio calculations indicate that water attachment onto CO2, N2O, and H2O is a thermodynamically favorable process, such that hydrated CO2·(H 2O)n, N2O(H2O)n, and H2O(H2O)n clusters would form a significant atmospheric repository of these species. Copyright 2008 by the American Geophysical Union.en_HK
dc.languageengen_HK
dc.publisherAmerican Geophysical Union.en_HK
dc.relation.ispartofJournal of Geophysical Researchen_HK
dc.rightsJournal of Geophysical Research. Copyright © American Geophysical Union.en_HK
dc.rightsCreative Commons: Attribution 3.0 Hong Kong License-
dc.subjectAb initio calculations-
dc.subjectAb initio investigation-
dc.subjectBulk water-
dc.subjectEnergetic properties-
dc.subjectHydration energies-
dc.titleAb initio investigation of the structure, stability, and atmospheric distribution of molecular clusters containing H2O, CO2, and N2Oen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0148-0227&volume=113&issue=19, article no. D19304&spage=&epage=&date=2008&atitle=Ab+initio+investigation+of+the+structure,+stability,+and+atmospheric+distribution+of+molecular+clusters+containing+H2O,+CO2,+and+N2Oen_HK
dc.identifier.emailLemke, KH: kono@hku.hken_HK
dc.identifier.authorityLemke, KH=rp00729en_HK
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.1029/2007JD009148en_HK
dc.identifier.scopuseid_2-s2.0-68149094359en_HK
dc.identifier.hkuros153268en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-68149094359&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume113en_HK
dc.identifier.issue19, article no. D19304en_HK
dc.identifier.eissn2169-8996-
dc.identifier.isiWOS:000259988200001-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridSeward, TM=7006454936en_HK
dc.identifier.scopusauthoridLemke, KH=24168776600en_HK

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