Journal
THEORETICAL CHEMISTRY ACCOUNTS
Volume 139, Issue 3, Pages -Publisher
SPRINGER
DOI: 10.1007/s00214-020-2555-6
Keywords
Protein electron transfer; Quantum chemistry; Nonadiabatic dynamics; Intersystem crossing
Categories
Funding
- Austrian Science Fund (FWF) [I2883]
- ANR [ANR-15-CE29-0027-01]
- Universidad de Alcala
Ask authors/readers for more resources
We present a computational study of sub-picosecond nonadiabatic dynamics in a rhenium complex coupled electronically to a tryptophan (Trp) side chain of Pseudomonas aeruginosa azurin, a prototypical protein used in the study of electron transfer in proteins. To gain a comprehensive understanding of the photoinduced processes in this system, we have carried out vertical excitation calculations at the TDDFT level of theory as well as nonadiabatic dynamics simulations using the surface hopping including arbitrary couplings (SHARC) method coupled to potential energy surfaces represented with a linear vibronic coupling model. The results show that the initial photoexcitation populates both singlet metal-to-ligand charge transfer (MLCT) and singlet charge-separated (CS) states, where in the latter an electron was transferred from the Trp amino acid to the complex. Subsequently, a complex mechanism of simultaneous intersystem crossing and electron transfer leads to the sub-picosecond population of triplet MLCT and triplet CS states. These results confirm the assignment of the sub-ps time constants of previous experimental studies and constitute the first computational evidence for the ultrafast formation of the charge-separated states in Re-sensitized azurin.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available