Photoelectron spectroscopic and theoretical study of the [HPd(eta(2)-H-2)]-cluster anion

摘要

Anion photoelectron spectroscopic and theoretical studies were conducted for the PdH- and PdH3cluster anions. Experimentally observed electron affinities and vertical detachment energies agree well with theoretical predictions. The PdH3- anionic complex is made up of a PdH- sub-anion ligated by a H-2 molecule, in which the H H bond is lengthened compared to free H-2. Detailed molecular orbital analysis of PdH-, H-2, and PdH3- reveals that back donation from a d-type orbital of PdH- to the sigma* orbital of H-2 causes the H H elongation, and hence, its activation. The H-2 binding energy to PdHis calculated to be 89.2 kJ/mol, which is even higher than that between CO and Pd. The unusually high binding energy as well as the H H bond activation may have practical applications, e.g., hydrogen storage and catalysis. (C) 2015 AIP Publishing LLC.