Effect of the Charge State on Bare monoicosahedral [Au13]z+ and diphospine-Protected Au13 clusters [Au13(dmpe)5Cl2]z+: a structural, electronic and vibrational DFT study
In this paper an electronic, structural and vibrational GGA-PBE study of positively charged Au13 bare clusters (z=+3, +5) and diphosphine protected [Au13(dmpe)5Cl2]z+ clusters (z=1, 3) is addressed. Moreover, we evaluate the adsorption energy of a cisplatin dimer interacting with the [Au13((P(CH3)2CH2)2)5Cl2]3+ complex (0.53 eV) to explore its application as a carrier/detector. We determine one Au13(dmpe)5Cl2 cluster with a 1+ charge featuring a slight reduced HOMO-LUMO gap, and one inner Au13 core heavily distorted (strong charge effects). It is found that the filling/distribution of the superatomic energy levels is affected by the addition of two electrons to the [Au13(dmpe)5Cl2]3+ cluster with a reduction of its symmetry (C1 point group). Calculated IR and Raman spectra of charged [Au13(dmpe)5Cl2]z+ clusters allow to distinguish among them.