Abstract
The previously derived trajectory-based nonadiabatic molecular dynamics scheme [E. Tapavicza, I. Tavernelli, U. Rothlisberger, Phys. Rev. Lett. 98 (2007) 023001] is extended to include the coupling of the quantum system with a classically described environment. The dynamics is performed using LR-TDDFT energies and forces computed on-the-fly together with the nonadiabatic coupling vectors needed for the propagation of the nuclear coefficients according to Tully's fewest-switches surface hopping algorithm. The resulting LR-TDDFT-QM/MM approach is applied to the study of the ultrafast relaxation of the photoexcited singlet metal-to-ligand-charge-transfer state (1MLCT) of [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) in water. The observed intersystem crossing dynamics with the triplet MLCT is in good agreement with available experimental results.
Original language | English |
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Pages (from-to) | 101-109 |
Number of pages | 9 |
Journal | Chemical Physics |
Volume | 391 |
Issue number | 1 |
DOIs | |
Publication status | Published - 24 Nov 2011 |
Keywords
- Inorganic dyes
- LR-TDDFT
- Nonadiabatic dynamics
- QM/MM
- Ruthenium (II) tris (bipyridine)
- Surface hopping