jp048360m_si_001.rtf (28.06 kB)
Spectroscopic Properties of [Pt2(μ-P2O5H2)4]:4- A Time-Dependent Density Functional Theory and Conductor-like Polarizable Continuum Model Investigation
dataset
posted on 2004-08-12, 00:00 authored by Stanislav R. Stoyanov, John M. Villegas, D. Paul RillemaThe calculation of the singlet ground-state (SGS) and the lowest-lying triplet-state (LLTS) geometries of
[Pt2(μ-P2O5H2)4]4- in the gas phase using density functional theory (DFT) produces 7% Pt−Pt bond shortening
in the LLTS as compared to SGS. The transition from the Pt−Pt antibonding HOMO to the bonding LUMO+1
in the gas phase and to the bonding LUMO in water creates a metal−metal σ bond in both excited states.
According to the molecular orbital population analysis in water performed using the conductor-like polarizable
continuum model (CPCM) and the SGS geometry, the Pt−Pt bond arises from the overlap of the metal p
orbitals. The singlet excited-state energy of 27 240 cm-1 in the gas phase is only 40 cm-1 higher than the
experimental absorption energy. The first triplet excited-state energy of 22 730 cm-1 in the gas phase and
22 810 cm-1 in water correlates with the experimental phosphorescence excitation energy of 22 100 cm-1.
The energy of the LLTS correlates with the experimental phosphorescence emission energy.
