Direct contact vs. solvent-shared ion pairs in nicl2 electrolytesmonitored by multiplet effects at the ni(ii) l-edge x-ray absorptionDOC_XNOTE=Published by BESSY, Germany in collaboration with LawrenceBerkeley National Laboratory staff.

We investigate the local electronic structure in aqueous NiCl{sub 2} electrolytes by Ni L edge x-ray absorption spectroscopy. The experimental findings are interpreted in conjunction with multiplet calculations of the electronic structure and the resulting spectral shape. In contrast to the situation in the solid, the electronic structure in the electrolyte reflects the absence of direct contact Ni-Cl ion pairs. We observe a systematic change of the intensity ratio of singlet and triplet-related spectral features as a function of electrolyte concentration. These changes can be described theoretically by a changed weight of transition matrix contributions with different symmetry. We interpret these findings as being due to progressive distortions of the local symmetry induced by solvent-shared ion pairs