Relation between the Widom line and the breakdown of the Stokes-Einstein relation in supercooled water
Supercooled water exhibits a breakdown of the Stokes-Einstein relation between the diffusion constant D and the alpha relaxation time τα. For water simulated with two different potentials, TIP5P and ST2, we find that the temperature of the decoupling of diffusion and alpha relaxation correlates with...
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| Veröffentlicht in: | Proceedings of the National Academy of Sciences - PNAS 2007-06, Vol.104 (23), p.9575-9579 |
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| container_title | Proceedings of the National Academy of Sciences - PNAS |
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| creator | Kumar, Pradeep Buldyrev, S.V Becker, S.R Poole, P.H Starr, F.W Stanley, H.E |
| description | Supercooled water exhibits a breakdown of the Stokes-Einstein relation between the diffusion constant D and the alpha relaxation time τα. For water simulated with two different potentials, TIP5P and ST2, we find that the temperature of the decoupling of diffusion and alpha relaxation correlates with the temperature of the maximum in specific heat that corresponds to crossing the Widom line TW(P). Specifically, we find that our results for Dτα/T collapse onto a single "master curve" if temperature is replaced by T - TW(P). We further find that the size of the mobile molecule clusters (dynamical heterogeneities) increases sharply near TW(P). Moreover, our calculations of mobile particle cluster size w for different pressures, where t* is the time for which the mobile particle cluster size is largest, also collapse onto a single master curve if T is replaced by T - TW(P). The crossover to a more locally structured low density liquid (LDL) as T [rightward arrow] TW(P) appears to be well correlated both with the breakdown of the Stokes-Einstein relation and with the growth of dynamic heterogeneities. Our results are consistent with the possibility that the breakdown of the SE relation in supercooled water at low pressures is associated with the hypothesized liquid-liquid phase transition. |
| doi_str_mv | 10.1073/pnas.0702608104 |
| format | Article |
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For water simulated with two different potentials, TIP5P and ST2, we find that the temperature of the decoupling of diffusion and alpha relaxation correlates with the temperature of the maximum in specific heat that corresponds to crossing the Widom line TW(P). Specifically, we find that our results for Dτα/T collapse onto a single "master curve" if temperature is replaced by T - TW(P). We further find that the size of the mobile molecule clusters (dynamical heterogeneities) increases sharply near TW(P). Moreover, our calculations of mobile particle cluster size <n(t*)>w for different pressures, where t* is the time for which the mobile particle cluster size is largest, also collapse onto a single master curve if T is replaced by T - TW(P). The crossover to a more locally structured low density liquid (LDL) as T [rightward arrow] TW(P) appears to be well correlated both with the breakdown of the Stokes-Einstein relation and with the growth of dynamic heterogeneities. Our results are consistent with the possibility that the breakdown of the SE relation in supercooled water at low pressures is associated with the hypothesized liquid-liquid phase transition.</description><identifier>ISSN: 0027-8424</identifier><identifier>EISSN: 1091-6490</identifier><identifier>DOI: 10.1073/pnas.0702608104</identifier><language>eng</language><publisher>Washington: National Academy of Sciences</publisher><subject>Cooling ; Critical points ; Critical temperature ; Crossovers ; Diffusion ; Experimental data ; Liquids ; Low pressure ; Molecules ; Physical Sciences ; Physics ; Size ; Specific heat ; Temperature ; Water ; Water temperature</subject><ispartof>Proceedings of the National Academy of Sciences - PNAS, 2007-06, Vol.104 (23), p.9575-9579</ispartof><rights>Copyright 2007 The National Academy of Sciences of the United States of America</rights><rights>Copyright National Academy of Sciences Jun 5, 2007</rights><rights>2007 by The National Academy of Sciences of the USA 2007</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c533t-e6bbe037d62c7a2f8b39ad5d3d6f12f44dcd59258ef8d481cfba8b75fb43d0b33</citedby><cites>FETCH-LOGICAL-c533t-e6bbe037d62c7a2f8b39ad5d3d6f12f44dcd59258ef8d481cfba8b75fb43d0b33</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Uhttp://www.pnas.org/content/104/23.cover.gif</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/25427901$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/25427901$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>230,314,724,777,781,800,882,27905,27906,53772,53774,57998,58231</link.rule.ids></links><search><creatorcontrib>Kumar, Pradeep</creatorcontrib><creatorcontrib>Buldyrev, S.V</creatorcontrib><creatorcontrib>Becker, S.R</creatorcontrib><creatorcontrib>Poole, P.H</creatorcontrib><creatorcontrib>Starr, F.W</creatorcontrib><creatorcontrib>Stanley, H.E</creatorcontrib><title>Relation between the Widom line and the breakdown of the Stokes-Einstein relation in supercooled water</title><title>Proceedings of the National Academy of Sciences - PNAS</title><description>Supercooled water exhibits a breakdown of the Stokes-Einstein relation between the diffusion constant D and the alpha relaxation time τα. For water simulated with two different potentials, TIP5P and ST2, we find that the temperature of the decoupling of diffusion and alpha relaxation correlates with the temperature of the maximum in specific heat that corresponds to crossing the Widom line TW(P). Specifically, we find that our results for Dτα/T collapse onto a single "master curve" if temperature is replaced by T - TW(P). We further find that the size of the mobile molecule clusters (dynamical heterogeneities) increases sharply near TW(P). Moreover, our calculations of mobile particle cluster size <n(t*)>w for different pressures, where t* is the time for which the mobile particle cluster size is largest, also collapse onto a single master curve if T is replaced by T - TW(P). The crossover to a more locally structured low density liquid (LDL) as T [rightward arrow] TW(P) appears to be well correlated both with the breakdown of the Stokes-Einstein relation and with the growth of dynamic heterogeneities. Our results are consistent with the possibility that the breakdown of the SE relation in supercooled water at low pressures is associated with the hypothesized liquid-liquid phase transition.</description><subject>Cooling</subject><subject>Critical points</subject><subject>Critical temperature</subject><subject>Crossovers</subject><subject>Diffusion</subject><subject>Experimental data</subject><subject>Liquids</subject><subject>Low pressure</subject><subject>Molecules</subject><subject>Physical Sciences</subject><subject>Physics</subject><subject>Size</subject><subject>Specific heat</subject><subject>Temperature</subject><subject>Water</subject><subject>Water temperature</subject><issn>0027-8424</issn><issn>1091-6490</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><recordid>eNp9kc1v1DAQxSMEEkvhzAkRceKSdvwVOxckVLWAVAmpH-Jo2fG4zTZrL7bDlv-ebHfZigunGc385s2TXlW9JXBMQLKTdTD5GCTQFhQB_qxaEOhI0_IOnlcLACobxSl_Wb3KeQkAnVCwqPwljqYMMdQWywYx1OUO6x-Di6t6HALWJrjHkU1o7l3chDr6x8FVifeYm7Mh5IJDqNNfobnP0xpTH-OIrt6Ygul19cKbMeObfT2qbs7Prk-_Nhffv3w7_XzR9IKx0mBrLQKTrqW9NNQryzrjhGOu9YR6zl3vREeFQq8cV6T31igrhbecObCMHVWfdrrrya7Q9RhKMqNep2Fl0m8dzaD_3YThTt_GX5ooJQVXs8CHvUCKPyfMRS_jlMLsWVMgTAjZtjN0soP6FHNO6A8PCOhtGHobhn4KY754v5fdLp5orinTnZBiJj7-n9B-GseCD2VG3-3QZS4xHVgqOJXdbPLwzJuozW0asr652roHkIpIEOwPKemrhQ</recordid><startdate>20070605</startdate><enddate>20070605</enddate><creator>Kumar, Pradeep</creator><creator>Buldyrev, S.V</creator><creator>Becker, S.R</creator><creator>Poole, P.H</creator><creator>Starr, F.W</creator><creator>Stanley, H.E</creator><general>National Academy of Sciences</general><general>National Acad Sciences</general><scope>FBQ</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QG</scope><scope>7QL</scope><scope>7QP</scope><scope>7QR</scope><scope>7SN</scope><scope>7SS</scope><scope>7T5</scope><scope>7TK</scope><scope>7TM</scope><scope>7TO</scope><scope>7U9</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>H94</scope><scope>M7N</scope><scope>P64</scope><scope>RC3</scope><scope>5PM</scope></search><sort><creationdate>20070605</creationdate><title>Relation between the Widom line and the breakdown of the Stokes-Einstein relation in supercooled water</title><author>Kumar, Pradeep ; 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For water simulated with two different potentials, TIP5P and ST2, we find that the temperature of the decoupling of diffusion and alpha relaxation correlates with the temperature of the maximum in specific heat that corresponds to crossing the Widom line TW(P). Specifically, we find that our results for Dτα/T collapse onto a single "master curve" if temperature is replaced by T - TW(P). We further find that the size of the mobile molecule clusters (dynamical heterogeneities) increases sharply near TW(P). Moreover, our calculations of mobile particle cluster size <n(t*)>w for different pressures, where t* is the time for which the mobile particle cluster size is largest, also collapse onto a single master curve if T is replaced by T - TW(P). The crossover to a more locally structured low density liquid (LDL) as T [rightward arrow] TW(P) appears to be well correlated both with the breakdown of the Stokes-Einstein relation and with the growth of dynamic heterogeneities. Our results are consistent with the possibility that the breakdown of the SE relation in supercooled water at low pressures is associated with the hypothesized liquid-liquid phase transition.</abstract><cop>Washington</cop><pub>National Academy of Sciences</pub><doi>10.1073/pnas.0702608104</doi><tpages>5</tpages><oa>free_for_read</oa></addata></record> |
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| subjects | Cooling Critical points Critical temperature Crossovers Diffusion Experimental data Liquids Low pressure Molecules Physical Sciences Physics Size Specific heat Temperature Water Water temperature |
| title | Relation between the Widom line and the breakdown of the Stokes-Einstein relation in supercooled water |
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