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) |
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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. |
doi_str_mv | 10.1063/5.0156573 |
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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.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/5.0156573</identifier><identifier>PMID: 37551810</identifier><identifier>CODEN: JCPSA6</identifier><language>eng</language><publisher>United States: American Institute of Physics</publisher><subject>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</subject><ispartof>The Journal of chemical physics, 2023-08, Vol.159 (6)</ispartof><rights>Author(s)</rights><rights>2023 Author(s). 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Our results may provide new insights into the dynamics of liquids and related phenomena such as liquid-glass and liquid-liquid phase transitions.</description><subject>Alcohols</subject><subject>Chemical reactions</subject><subject>Correlation</subject><subject>Coupling (molecular)</subject><subject>Dielectric relaxation</subject><subject>Diffractive optics</subject><subject>Inhomogeneity</subject><subject>Liquid phases</subject><subject>Liquids</subject><subject>Melting points</subject><subject>Phase transitions</subject><subject>Photons</subject><subject>Room temperature</subject><subject>Solvation</subject><subject>Time constant</subject><subject>Time correlation functions</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><recordid>eNp90E9LwzAYBvAgipvTg19AAl5U6HzTNEl7lOE_GHhQL15Kmya0s2tq0qr99sZ1evDgKZD8ePK-D0LHBOYEOL1kcyCMM0F30JRAnASCJ7CLpgAhCRIOfIIOnFsBABFhtI8mVDBGYgJT9PJYmw_sTP2edZVpcDE02bqSDudqME2Bi0rVSna2ktiqOvscVT7grrRKBW1fO4Xb0nT-VsnS4FZlr9iVle4O0Z7O_PPR9pyh55vrp8VdsHy4vV9cLQNJY9oFWog8FyyihDMKkSwESD8zCSWP8kSTJKGJjrSIKYtyv6ZmTHMhpOJ5GBdA6AydjbmtNW-9cl26rpxUdZ01yvQuDeNIiCghVHh6-oeuTG8bP91GMf8FUK_ORyWtcc4qnba2Wmd2SAmk34WnLN0W7u3JNrHP16r4lT8Ne3AxAierbtPeP2lfCUaGrg</recordid><startdate>20230814</startdate><enddate>20230814</enddate><creator>Kim, JunWoo</creator><creator>Shin, Pyoungsik</creator><creator>Joo, Taiha</creator><general>American Institute of Physics</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0009-0002-4660-0047</orcidid><orcidid>https://orcid.org/0000-0002-2269-757X</orcidid><orcidid>https://orcid.org/0000-0003-2690-7789</orcidid></search><sort><creationdate>20230814</creationdate><title>Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift</title><author>Kim, JunWoo ; Shin, Pyoungsik ; Joo, Taiha</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c383t-f77bb7543165304cd70c96012c64b9f19939f4f78354b156f55f677ce6b28d013</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2023</creationdate><topic>Alcohols</topic><topic>Chemical reactions</topic><topic>Correlation</topic><topic>Coupling (molecular)</topic><topic>Dielectric relaxation</topic><topic>Diffractive optics</topic><topic>Inhomogeneity</topic><topic>Liquid phases</topic><topic>Liquids</topic><topic>Melting points</topic><topic>Phase transitions</topic><topic>Photons</topic><topic>Room temperature</topic><topic>Solvation</topic><topic>Time constant</topic><topic>Time correlation functions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kim, JunWoo</creatorcontrib><creatorcontrib>Shin, Pyoungsik</creatorcontrib><creatorcontrib>Joo, Taiha</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kim, JunWoo</au><au>Shin, Pyoungsik</au><au>Joo, Taiha</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Slow solvation dynamics beyond dielectric relaxation by three-pulse photon echo peak shift</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2023-08-14</date><risdate>2023</risdate><volume>159</volume><issue>6</issue><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>The dynamics of a liquid and its coupling to a solute are crucial for a better understanding of chemical processes in the liquid phase. 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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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