Decoherence and vibrational energy relaxation of the electronically excited PtPOP complex in solution

Understanding the ultrafast vibrational relaxation following photoexcitation of molecules in a condensed phase is essential to predict the outcome and improve the efficiency of photoinduced molecular processes. Here, the vibrational decoherence and energy relaxation of a binuclear complex, [ Pt 2 ( P 2 O 5 H 2 ) 4 ] 4 − (PtPOP), upon electronic excitation in liquid water and acetonitrile are investigated through direct adiabatic dynamics simulations. A quantum mechanics/molecular mechanics (QM/MM) scheme is used where the excited state of the complex is modeled with orbital-optimized density functional calculations while solvent molecules are described using potential energy functions. The decoherence time of the Pt-Pt vibration dominating the photoinduced dynamics is found to be ∼1.6 ps in both solvents. This is in excellent agreement with experimental measurements in water, where intersystem crossing is slow ( > 10 ps). Pathways for the flow of excess energy are identified by monitoring the power of the solvent on vibrational modes. The latter are obtained as generalized normal modes from the velocity covariances, and the power is computed using QM/MM embedding forces. Excess vibrational energy is found to be predominantly released through short-range repulsive and attractive interactions between the ligand atoms and surrounding solvent molecules, whereas solute-solvent interactions involving the Pt atoms are less important. Since photoexcitation deposits most of the excess energy into Pt-Pt vibrations, energy dissipation to the solvent is inefficient. This study reveals the mechanism behind the exceptionally long vibrational coherence of the photoexcited PtPOP complex in solution and underscores the importance of short-range interactions for accurate simulations of vibrational energy relaxation of solvated molecules.