Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift

The dynamics of a liquid and its coupling to a solute are crucial for a better understanding of chemical processes in the liquid phase. In isotropic and homogeneous solutions, the time-correlation function of a solute is expected to vanish over time due to the translational and diffusive motions of...

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Veröffentlicht in:The Journal of chemical physics 2023-08, Vol.159 (6)
Hauptverfasser: Kim, JunWoo, Shin, Pyoungsik, Joo, Taiha
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container_title The Journal of chemical physics
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creator Kim, JunWoo
Shin, Pyoungsik
Joo, Taiha
description The dynamics of a liquid and its coupling to a solute are crucial for a better understanding of chemical processes in the liquid phase. In isotropic and homogeneous solutions, the time-correlation function of a solute is expected to vanish over time due to the translational and diffusive motions of the solvent. The three-pulse photon echo peak shift (3PEPS) is a third-order nonlinear spectroscopy technique that records the time-correlation function of a solute molecule in a solution, including an offset (inhomogeneity). In this work, we utilized a diffractive optics-based 3PEPS apparatus to fully resolve the dynamics in liquids from femtoseconds to nanoseconds while varying the temperature in the range of 80–298 K and the probe solute molecules. Our observations reveal dynamics slower than the dielectric relaxation of n-alcohols, even at room temperature, consisting of a ∼0.5 ns time constant that persists below the melting points and a static component (offset) on a nanosecond timescale. Based on the experiments, we suggest that locally formed glass-like clusters in liquids can be responsible for the slow dynamics. Our results may provide new insights into the dynamics of liquids and related phenomena such as liquid-glass and liquid-liquid phase transitions.
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source AIP Journals Complete; Alma/SFX Local Collection
subjects Alcohols
Chemical reactions
Correlation
Coupling (molecular)
Dielectric relaxation
Diffractive optics
Inhomogeneity
Liquid phases
Liquids
Melting points
Phase transitions
Photons
Room temperature
Solvation
Time constant
Time correlation functions
title Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift
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