Photoelectron spectroscopic and theoretical study of the [HPd(η2-H2)]− cluster anion

Paul J. Robinson, Gerd Ganteför, Anastassia Alexandrova, Kit H. Bowen
2015 Journal of Chemical Physics  
Vibrationally resolved photoelectron imaging of gold hydride cluster anions: AuH − and Au 2 H − Electronic and geometric structures of Co 2 C n − and V 2 C n − : Initial growth mechanisms of late and early 3d transition-metal carbide clusters Anion photoelectron spectroscopic and theoretical studies were conducted for the PdH − and PdH − 3 cluster anions. Experimentally observed electron affinities and vertical detachment energies agree well with theoretical predictions. The PdH − 3 anionic
more » ... PdH − 3 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 PdH − 3 reveals that back donation from a d-type orbital of PdH − to the σ* orbital of H 2 causes the H-H elongation, and hence, its activation. The H 2 binding energy to PdH − is 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. [http://dx.
doi:10.1063/1.4929998 pmid:26342370 fatcat:a2v5jf37xnhsvmnct6ipqnezka