Proton transfer or hemibonding? The structure and stability of radical cation clusters
Do, Hainam; Besley, Nicholas A.
Nicholas A. Besley
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|
|Publisher||Royal Society of Chemistry|
|Peer Reviewed||Peer Reviewed|
|APA6 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|
|Keywords||hemibonding, proton transfer, molecular clusters|
|Copyright Statement||Copyright information regarding this work can be found at the following address: http://eprints.nottingh.../end_user_agreement.pdf|
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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