An integral equation theory for solvation effects on the molecular structural fluctuation

Dynamics theories for molecular liquids based on an interaction site model have been developed over the past few decades and proved to be powerful tools to investigate various dynamical phenomena. In many of these theories, equations of time correlation functions are formulated by using the Zwanzig-Mori projection operator. Since algebriac equations are directly treated in these statistical mechanical approaches, the obtained dynamical properties are essentially free from statistical error. This perspective presents the theoretical framework of such theories and their applications, including visualization of diffusion processes, collective excitations, solvation dynamics, transport properties, and diffusion controlled reactions.

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Effects of intramolecular chain conformation on the hydration and miscibility of polyethylene glycol in water studied by means of polymer reference interaction site model theory

Yamaguchi

Chong

Yoshida

2023

The Journal of Chemical Physics

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To examine the conventional idea that the gauche conformation of the OCCO dihedral angle promotes the dissolution of polyethylene glycol (PEG) in water through strong hydration, the thermodynamic properties of liquid mixtures of PEG and water were studied by means of polymer reference interaction site model (PRISM) theory. The intramolecular correlation functions required as input for PRISM theory were calculated by the generator matrix method, accompanied by changes in the distribution of dihedral angles. In the infinite dilution limit, the increased probability of gauche conformation of the OCCO dihedral angles stabilizes the hydration of PEG through enhanced hydrogen bonding between the ether oxygen of PEG and water. The mixing Gibbs energies of the liquid mixtures were also calculated in the whole concentration range based on the Gibbs–Duhem equation, as per our recent proposal. A liquid–liquid phase separation was observed when all the dihedral angles of PEG were in the trans conformation; for the liquid mixture to be miscible in the whole concentration range, the introduction of the OCCO gauche conformation was found to be indispensable. The above theoretical results support the conventional idea that the OCCO gauche conformation is important for the high miscibility of PEG and water.

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An integral equation theory for solvation effects on the molecular structural fluctuation

Cited by 4 publications

References 46 publications

Theoretical Approach to Chemical Reactions and Photochemical Processes in Ionic Liquid

Theoretical Approach to Chemical Reactions and Photochemical Processes in Ionic Liquid

Dynamics theory for molecular liquids based on an interaction site model

Effects of intramolecular chain conformation on the hydration and miscibility of polyethylene glycol in water studied by means of polymer reference interaction site model theory

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