Solvent dynamics and electrostatic field fluctuations affect electron hoping dynamics

Our recent work in PNAS ‘Photoinduced hole hopping through tryptophans in proteins‘ presents a thorough investigation of water dynamics and electrostatic field fluctuations on the electron (hole) hopping dynamics in two rhenium-modified azurins. The research was done in collaboration with our excellent colleagues at Caltech, Queen Mary University of London, and Heyrovsky Institute of Czech Academy of Sciences.
We have employed QM/MM/MD TD-DFT dynamics on ps-timescales, which were complemented by advanced QM-analysis in the vicinity of electronic state crossing points. Accounting for explicit (MM) solvent we have described that the local hydration of key residues and ligands, which are involved in electron transport, fluctuates in time. Our results revealed that the electron hopping occurs, when the intrinsic hydration of TRP residue is not optimal for the initial electronic state, and instead resembles the hydration of the final state. Consequently, when the electron hop is attempted, the solvent environment is ready to stabilize it. In more generalized view, the electrostatic field fluctuations are good measures to judge if the system is approaching the electronic state crossing region.

Enjoy reading of our manuscript and if you are really interested check also our extensive SI.-)

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Thermodynamic insight in the hydration of a single guanidinium cation

Schematic temperature and pressure response of guanidinium cation hydration to increased temperatures and pressures.

We have employed extensive densimetry measurements of guanidinium chloride at UCT Prague, and performed MD simulations at UCT Prague, IOCB Prague, and at Ruđer Bošković Institute, Zagreb. We have collected data on temperature and pressure response of guanidinium chloride hydration, allowing us to determine volumetric properties at infinite dilution, i.e., at single ion limit.
We have clearly demonstrated this response is anomalous, on the half way between ordinary ions (e.g. sodium) and hydrophobic molecules (e.g. benzene). Employing directional analysis and Kirkwood-Buff theory, MD simulations point to hydrophobe-like hydration of quasi-aromatic faces and ion-like hydration of in-plane NH2 moieties. Enjoy the reading of our paper in the ‘Battino and Wilhelm’ Special Issue of the Journal of Chemical Thermodynamics. link

Multiyear allocation at IT4I supercomputers granted

We are happy that we have received within 21st OPEN call 1150k CPUhrs for computational support of our GACR (Insight in preferential interactions, bridging, and cononsolvency on PNIPAM). Me and my students, we are looking forward to using Barbora and other supercomputers. Thank you IT4I!