Counter-ion perturbation of the fragmentation pathways of multiply charged anions: evidence for exit channel complexes on the fragmentation potential energy surfaces

Ruth M Burke; William E Boxford; Caroline E H Dessent

doi:10.1063/1.2219116

Counter-ion perturbation of the fragmentation pathways of multiply charged anions: evidence for exit channel complexes on the fragmentation potential energy surfaces

J Chem Phys. 2006 Jul 14;125(2):21105. doi: 10.1063/1.2219116.

Authors

Ruth M Burke¹, William E Boxford, Caroline E H Dessent

Affiliation

¹ Department of Chemistry, University of York, Heslington, York YO10 5DD, United Kingdom.

PMID: 16848570
DOI: 10.1063/1.2219116

Abstract

We report the first low-energy collisional excitation measurements and density functional theory calculations to characterize the ground state potential energy surfaces of contact ion-pair complexes that contain multiply charged anions (MCAs). Excitation of K+.Pt(CN)(4) (2-) and K+.Pt(CN)(6) (2-) result in fragmentation products associated with decay of the isolated constituent dianions, revealing that the ground state ion-pair surfaces are dominated by the intrinsic characteristics of the MCA. This observation is important since it indicates that counter-ion complexation only weakly perturbs the electronic structure of an MCA. For K+.Pt(CN)(4) (2-), where the Pt(CN)(4) (2-) dianion decays with production of two ionic fragments, we observe evidence for the existence of a novel exit-channel complex corresponding to a polar KCN salt unit bound to the Pt(CN)(3) (-) anion. The results described provide a basis for understanding the potential energy surfaces and fragmentation characteristics of other ion-pair complexes that involve MCAs.