Structures and electronic spectra of [Pt2(P2O5H2)4X2]4− (X = Cl, Br and I): A comparative study of ab initio and density functional theory

The structures of [Pt2(P2O5H2)4X2]4− (X = Cl (1), Br (2) and I (3)) were optimized using the ab initio and density functional theory methods. It is shown that the geometry parameters estimated by MP2 and XαVWN are closer to experimental values. We performed the time-dependent density functional theory (TD-DFT) calculations to explore the influence of different density functionals and structures on electronic absorption spectra in solution. The experimental absorptions with the featured σ(dz2)→σ∗(dz2)σ(dz2)→σ∗(dz2) and π(dxz,dyz)→σ∗(dz2)π(dxz,dyz)→σ∗(dz2) transitions are well reproduced by the theoretical calculations.

Graphical abstractStructures and electronic spectra of [Pt2(P2O5H2)4X2]4− (X = Cl (1), Br (2) and I (3)) were explored at the ab initio and density functional theory levels. The studies focusing on the σ → σ∗ and π → σ∗ transitions reveal that a reasonable structure associated with an alternative time-dependent density functional is very necessary to obtain the precise transition energy.Figure optionsDownload full-size imageDownload as PowerPoint slide