The role of memory-dependent friction and solvent viscosity in isomerization kinetics in visco-genic media

The role of memory-dependent friction and solvent viscosity in isomerization kinetics in visco-genic media

04 May 2024 | Benjamin A. Dalton, Henrik Kiefer & Roland R. Netz
This study investigates the role of memory-dependent friction and solvent viscosity in isomerization kinetics in viscogenic media. Using molecular dynamics simulations and friction memory-kernel extraction techniques, the researchers analyze the isomerization of small molecules under various viscogenic conditions. They find that the influence of different viscogenic media on isomerization kinetics can be dramatically different, even when measured at the same viscosity. This is due to dynamic solute-solvent coupling mediated by time-dependent friction memory kernels. The study reveals that deviations from the linear dependence of isomerization rates on solvent viscosity are not solely due to internal friction effects but also result from violations of the Stokes-Einstein relation and the overdamped Kramers prediction for barrier-crossing rates. The research shows that molecular conformational transition rates, such as photoisomerization rates or protein folding rates, are influenced by interactions between the molecule and its solvent environment. The study demonstrates that the isomerization times of small molecules like butane exhibit different viscosity scaling depending on the solvent type and composition. The results indicate that the Stokes-Einstein relation is generally violated for dihedral isomerization, and the specific deviations from the friction-viscosity relationship depend on the choice of reaction coordinate. The study also reveals that the isomerization kinetics of larger molecules, such as decane or amino acids, appear to converge between different solvation methods, especially in the lower viscosity regime. The results highlight the importance of solvent composition and solute size in determining the relationships between dihedral friction, solvent viscosity, and isomerization kinetics. The findings suggest that non-Markovian friction effects play a crucial role in the dynamics of molecular reconfiguration in complex viscogenic media. The study provides insights into the multi-time-scale non-Markovian dynamics of dihedral isomerization in viscous solvents, emphasizing the importance of memory-induced speed-up effects in isomerization kinetics.This study investigates the role of memory-dependent friction and solvent viscosity in isomerization kinetics in viscogenic media. Using molecular dynamics simulations and friction memory-kernel extraction techniques, the researchers analyze the isomerization of small molecules under various viscogenic conditions. They find that the influence of different viscogenic media on isomerization kinetics can be dramatically different, even when measured at the same viscosity. This is due to dynamic solute-solvent coupling mediated by time-dependent friction memory kernels. The study reveals that deviations from the linear dependence of isomerization rates on solvent viscosity are not solely due to internal friction effects but also result from violations of the Stokes-Einstein relation and the overdamped Kramers prediction for barrier-crossing rates. The research shows that molecular conformational transition rates, such as photoisomerization rates or protein folding rates, are influenced by interactions between the molecule and its solvent environment. The study demonstrates that the isomerization times of small molecules like butane exhibit different viscosity scaling depending on the solvent type and composition. The results indicate that the Stokes-Einstein relation is generally violated for dihedral isomerization, and the specific deviations from the friction-viscosity relationship depend on the choice of reaction coordinate. The study also reveals that the isomerization kinetics of larger molecules, such as decane or amino acids, appear to converge between different solvation methods, especially in the lower viscosity regime. The results highlight the importance of solvent composition and solute size in determining the relationships between dihedral friction, solvent viscosity, and isomerization kinetics. The findings suggest that non-Markovian friction effects play a crucial role in the dynamics of molecular reconfiguration in complex viscogenic media. The study provides insights into the multi-time-scale non-Markovian dynamics of dihedral isomerization in viscous solvents, emphasizing the importance of memory-induced speed-up effects in isomerization kinetics.
Reach us at info@study.space
[slides and audio] The role of memory-dependent friction and solvent viscosity in isomerization kinetics in viscogenic media