Electron density topological and adsorbate orbital analyses of water and carbon monoxide co-adsorption on platinum.

The electron density topology of carbon monoxide (CO) on dry and hydrated platinum is evaluated under the quantum theory of atoms in molecules (QTAIM) and by adsorbate orbital approaches. The impact of water co-adsorbate on the electronic, structural, and vibrational properties of CO on Pt are modelled by periodic density functional theory (DFT). At low CO coverage, increased hydration weakens C-O bonds and strengthens C-Pt bonds, as verified by changes in bond lengths and stretching frequencies. These results are consistent with QTAIM, the 5σ donation-2π backdonation model, and our extended π-attraction -repulsion model (extended π- model). This work links changes in the non-zero eigenvalues of the electron density Hessian at QTAIM bond critical points to changes in the π and C-O bonds with systematic variation of CO/HO co-adsorbate scenarios. QTAIM invariably shows bond strengths and lengths as being negatively correlated. For atop CO on hydrated Pt, QTAIM and phenomenological models are consistent with a direct correlation between C-O bond strength and CO coverage. However, DFT modelling in the absence of hydration shows that C-O bond lengths are not negatively correlated to their stretching frequencies, in contrast to the Badger rule: When QTAIM and phenomenological models do not agree, the use of the non-zero eigenvalues of the electron density Hessian as inputs to the phenomenological models, aligns them with QTAIM. The C-O and C-Pt bond strengths of bridge and three-fold bound CO on dry and hydrated platinum are also evaluated by QTAIM and adsorbate orbital analyses.