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Proton transfer or hemibonding? The structure and stability of radical cation clusters

Do, Hainam; Besley, Nicholas A.

Authors

Hainam Do

Nicholas A. Besley

Abstract

The basin hopping search algorithm in conjunction with second-order Moller-Plesset perturbation theory is used to determine the lowest energy structures of the radical cation clusters (NH_3)_n^+, (H_2O)_n^+, (HF)_n^+, (PH_3)_n^+, (H_2S)_n^+ and (HCl)_n^+, where n=2-4. The energies of the most stable structures are subsequently evaluated using coupled cluster theory in conjunction with the aug-cc-pVTZ basis set. These cationic clusters can adopt two distinct structural types, with some clusters showing an unusual type of bonding, often referred to as hemibonding, while other clusters undergo proton transfer to give an ion and radical. It is found that proton transfer based structures are preferred by the (NH_3)_n+, (H_2O)_n^+, and (HF)_n^+ clusters while hemibonded structures are favoured by (PH_3)_n^+, (H_2S)_n^+ and (HCl)_n^+. These trends can be attributed to the relative strengths of the molecules and molecular cations as Brønsted bases and acids, respectively, and the strength of the interaction between the ion and radical in the ion-radical clusters.

Journal Article Type Article
Publication Date Aug 22, 2013
Journal Physical Chemistry Chemical Physics
Print ISSN 1463-9076
Electronic ISSN 1463-9076
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 15
Institution Citation Do, H., & Besley, N. A. (2013). Proton transfer or hemibonding? The structure and stability of radical cation clusters. Physical Chemistry Chemical Physics, 15, doi:10.1039/C3CP52922C
DOI https://doi.org/10.1039/C3CP52922C
Keywords hemibonding, proton transfer, molecular clusters
Publisher URL http://pubs.rsc.org/en/content/articlelanding/2013/cp/c3cp52922c#!divAbstract
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf




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