Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions
We present an ab initio molecular dynamics study of the alkali metal ions Li + , Na + , K + and Cs + , and of the alkaline earth metal ions Mg 2+ and Ca 2+ in both pure water and electrolyte solutions containing the counterions Cl − and SO 4 2− . Simulations were conducted using different density fu...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2020-07, Vol.22 (28), p.1631-16313 |
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| creator | Wang, Xiangwen Toroz, Dimitrios Kim, Seonmyeong Clegg, Simon L Park, Gun-Sik Di Tommaso, Devis |
| description | We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
. Simulations were conducted using different density functional theory methods (PBE, BLYP and revPBE), with and without the inclusion of dispersion interactions (-D3). Analysis of the ion-water structure and interaction strength, water exchange between the first and second hydration shell, and hydrogen bond network and low-frequency reorientation dynamics around the metal ions have been used to characterise the influence of solution composition on the ionic solvation shell. Counterions affect the properties of the hydration shell not only when they are directly coordinated to the metal ion, but also when they are at the second coordination shell. Chloride ions reduce the sodium hydration shell and expand the calcium hydration shell by stabilizing under-coordinated hydrated Na(H
2
O)
5
+
complexes and over-coordinated Ca(H
2
O)
7
2+
. The same behaviour is observed in CaSO
4
(aq), where Ca
2+
and SO
4
2−
form almost exclusively solvent-shared ion pairs. Water exchange between the first and second hydration shell around Ca
2+
in CaSO
4
(aq) is drastically decelerated compared with the simulations of the hydrated metal ion (single Ca
2+
, no counterions). Velocity autocorrelation function analysis, used to probe the strength of the local ion-water interaction, shows a smoother decay of Mg
2+
in MgCl
2
(aq), which is a clear indication of a looser inter-hexahedral vibration in the presence of chloride ions located in the second coordination shell of Mg
2+
. The hydrogen bond statistics and orientational dynamics in the ionic solvation shell show that the influence on the water-water network cannot only be ascribed to the specific cation-water interaction, but also to the subtle interplay between the level of hydration of the ions, and the interactions between ions, especially those of opposite charge. As many reactive processes involving solvated metal ions occur in environments that are far from pure water but rich in ions, this computational study shows how the solution composition can result in significant differences in behaviour and function of the ionic solvation shell.
We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+ |
| doi_str_mv | 10.1039/d0cp01957g |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_2423060728</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2423060728</sourcerecordid><originalsourceid>FETCH-LOGICAL-c520t-8aa7b58e873a914759458d73348b78614bdb2bc73bd9930a29c5484cc789e6043</originalsourceid><addsrcrecordid>eNp9kc9LwzAcxYsoOKcX70LEiwjTpEma5Cibv2CgBz2XNE1dR9vUfFuhB_93000mePCUR97n-xK-L4pOCb4mmKqbHJsWE8XF-140ISyhM4Ul299pkRxGRwBrjDHhhE6ir4VtoOwGVPSN6UrX6Ap1K-v8gDINNke1q6zpK-1RPjS6Lg0g6Pp8QK5A4Kp-nEHG1a0LMaO2RWFNByjIEDQyn3pjwMpW1ThW2y68Eq7gODoodAX25OecRm_3d6_zx9ny-eFpfrucGR7jbia1FhmXVgqqFWGCK8ZlLihlMhMyISzLszgzgma5UhTrWBnOJDNGSGUTzOg0utzmtt599Ba6tC7BhO_oxroe0pjFFCdYxDKgF3_Qtet9WMuGSnjYIx-pqy1lvAPwtkhbX9baDynB6dhEusDzl00TDwE-28IezI77bSr45__5aZsX9Bto_JIY</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2426546358</pqid></control><display><type>article</type><title>Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Wang, Xiangwen ; Toroz, Dimitrios ; Kim, Seonmyeong ; Clegg, Simon L ; Park, Gun-Sik ; Di Tommaso, Devis</creator><creatorcontrib>Wang, Xiangwen ; Toroz, Dimitrios ; Kim, Seonmyeong ; Clegg, Simon L ; Park, Gun-Sik ; Di Tommaso, Devis</creatorcontrib><description>We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
. Simulations were conducted using different density functional theory methods (PBE, BLYP and revPBE), with and without the inclusion of dispersion interactions (-D3). Analysis of the ion-water structure and interaction strength, water exchange between the first and second hydration shell, and hydrogen bond network and low-frequency reorientation dynamics around the metal ions have been used to characterise the influence of solution composition on the ionic solvation shell. Counterions affect the properties of the hydration shell not only when they are directly coordinated to the metal ion, but also when they are at the second coordination shell. Chloride ions reduce the sodium hydration shell and expand the calcium hydration shell by stabilizing under-coordinated hydrated Na(H
2
O)
5
+
complexes and over-coordinated Ca(H
2
O)
7
2+
. The same behaviour is observed in CaSO
4
(aq), where Ca
2+
and SO
4
2−
form almost exclusively solvent-shared ion pairs. Water exchange between the first and second hydration shell around Ca
2+
in CaSO
4
(aq) is drastically decelerated compared with the simulations of the hydrated metal ion (single Ca
2+
, no counterions). Velocity autocorrelation function analysis, used to probe the strength of the local ion-water interaction, shows a smoother decay of Mg
2+
in MgCl
2
(aq), which is a clear indication of a looser inter-hexahedral vibration in the presence of chloride ions located in the second coordination shell of Mg
2+
. The hydrogen bond statistics and orientational dynamics in the ionic solvation shell show that the influence on the water-water network cannot only be ascribed to the specific cation-water interaction, but also to the subtle interplay between the level of hydration of the ions, and the interactions between ions, especially those of opposite charge. As many reactive processes involving solvated metal ions occur in environments that are far from pure water but rich in ions, this computational study shows how the solution composition can result in significant differences in behaviour and function of the ionic solvation shell.
We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d0cp01957g</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Alkali metals ; Alkaline earth metals ; Autocorrelation functions ; Calcium ions ; Chloride ions ; Composition effects ; Computer simulation ; Coordination ; Deceleration ; Density functional theory ; Function analysis ; Hydration ; Hydrogen bonds ; Ion pairs ; Ions ; Magnesium chloride ; Metal ions ; Molecular dynamics ; Simulation ; Sodium ; Solvation ; Time correlation functions</subject><ispartof>Physical chemistry chemical physics : PCCP, 2020-07, Vol.22 (28), p.1631-16313</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c520t-8aa7b58e873a914759458d73348b78614bdb2bc73bd9930a29c5484cc789e6043</citedby><cites>FETCH-LOGICAL-c520t-8aa7b58e873a914759458d73348b78614bdb2bc73bd9930a29c5484cc789e6043</cites><orcidid>0000-0002-4485-4468</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Wang, Xiangwen</creatorcontrib><creatorcontrib>Toroz, Dimitrios</creatorcontrib><creatorcontrib>Kim, Seonmyeong</creatorcontrib><creatorcontrib>Clegg, Simon L</creatorcontrib><creatorcontrib>Park, Gun-Sik</creatorcontrib><creatorcontrib>Di Tommaso, Devis</creatorcontrib><title>Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions</title><title>Physical chemistry chemical physics : PCCP</title><description>We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
. Simulations were conducted using different density functional theory methods (PBE, BLYP and revPBE), with and without the inclusion of dispersion interactions (-D3). Analysis of the ion-water structure and interaction strength, water exchange between the first and second hydration shell, and hydrogen bond network and low-frequency reorientation dynamics around the metal ions have been used to characterise the influence of solution composition on the ionic solvation shell. Counterions affect the properties of the hydration shell not only when they are directly coordinated to the metal ion, but also when they are at the second coordination shell. Chloride ions reduce the sodium hydration shell and expand the calcium hydration shell by stabilizing under-coordinated hydrated Na(H
2
O)
5
+
complexes and over-coordinated Ca(H
2
O)
7
2+
. The same behaviour is observed in CaSO
4
(aq), where Ca
2+
and SO
4
2−
form almost exclusively solvent-shared ion pairs. Water exchange between the first and second hydration shell around Ca
2+
in CaSO
4
(aq) is drastically decelerated compared with the simulations of the hydrated metal ion (single Ca
2+
, no counterions). Velocity autocorrelation function analysis, used to probe the strength of the local ion-water interaction, shows a smoother decay of Mg
2+
in MgCl
2
(aq), which is a clear indication of a looser inter-hexahedral vibration in the presence of chloride ions located in the second coordination shell of Mg
2+
. The hydrogen bond statistics and orientational dynamics in the ionic solvation shell show that the influence on the water-water network cannot only be ascribed to the specific cation-water interaction, but also to the subtle interplay between the level of hydration of the ions, and the interactions between ions, especially those of opposite charge. As many reactive processes involving solvated metal ions occur in environments that are far from pure water but rich in ions, this computational study shows how the solution composition can result in significant differences in behaviour and function of the ionic solvation shell.
We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
.</description><subject>Alkali metals</subject><subject>Alkaline earth metals</subject><subject>Autocorrelation functions</subject><subject>Calcium ions</subject><subject>Chloride ions</subject><subject>Composition effects</subject><subject>Computer simulation</subject><subject>Coordination</subject><subject>Deceleration</subject><subject>Density functional theory</subject><subject>Function analysis</subject><subject>Hydration</subject><subject>Hydrogen bonds</subject><subject>Ion pairs</subject><subject>Ions</subject><subject>Magnesium chloride</subject><subject>Metal ions</subject><subject>Molecular dynamics</subject><subject>Simulation</subject><subject>Sodium</subject><subject>Solvation</subject><subject>Time correlation functions</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kc9LwzAcxYsoOKcX70LEiwjTpEma5Cibv2CgBz2XNE1dR9vUfFuhB_93000mePCUR97n-xK-L4pOCb4mmKqbHJsWE8XF-140ISyhM4Ul299pkRxGRwBrjDHhhE6ir4VtoOwGVPSN6UrX6Ap1K-v8gDINNke1q6zpK-1RPjS6Lg0g6Pp8QK5A4Kp-nEHG1a0LMaO2RWFNByjIEDQyn3pjwMpW1ThW2y68Eq7gODoodAX25OecRm_3d6_zx9ny-eFpfrucGR7jbia1FhmXVgqqFWGCK8ZlLihlMhMyISzLszgzgma5UhTrWBnOJDNGSGUTzOg0utzmtt599Ba6tC7BhO_oxroe0pjFFCdYxDKgF3_Qtet9WMuGSnjYIx-pqy1lvAPwtkhbX9baDynB6dhEusDzl00TDwE-28IezI77bSr45__5aZsX9Bto_JIY</recordid><startdate>20200722</startdate><enddate>20200722</enddate><creator>Wang, Xiangwen</creator><creator>Toroz, Dimitrios</creator><creator>Kim, Seonmyeong</creator><creator>Clegg, Simon L</creator><creator>Park, Gun-Sik</creator><creator>Di Tommaso, Devis</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-4485-4468</orcidid></search><sort><creationdate>20200722</creationdate><title>Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions</title><author>Wang, Xiangwen ; Toroz, Dimitrios ; Kim, Seonmyeong ; Clegg, Simon L ; Park, Gun-Sik ; Di Tommaso, Devis</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c520t-8aa7b58e873a914759458d73348b78614bdb2bc73bd9930a29c5484cc789e6043</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Alkali metals</topic><topic>Alkaline earth metals</topic><topic>Autocorrelation functions</topic><topic>Calcium ions</topic><topic>Chloride ions</topic><topic>Composition effects</topic><topic>Computer simulation</topic><topic>Coordination</topic><topic>Deceleration</topic><topic>Density functional theory</topic><topic>Function analysis</topic><topic>Hydration</topic><topic>Hydrogen bonds</topic><topic>Ion pairs</topic><topic>Ions</topic><topic>Magnesium chloride</topic><topic>Metal ions</topic><topic>Molecular dynamics</topic><topic>Simulation</topic><topic>Sodium</topic><topic>Solvation</topic><topic>Time correlation functions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wang, Xiangwen</creatorcontrib><creatorcontrib>Toroz, Dimitrios</creatorcontrib><creatorcontrib>Kim, Seonmyeong</creatorcontrib><creatorcontrib>Clegg, Simon L</creatorcontrib><creatorcontrib>Park, Gun-Sik</creatorcontrib><creatorcontrib>Di Tommaso, Devis</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wang, Xiangwen</au><au>Toroz, Dimitrios</au><au>Kim, Seonmyeong</au><au>Clegg, Simon L</au><au>Park, Gun-Sik</au><au>Di Tommaso, Devis</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><date>2020-07-22</date><risdate>2020</risdate><volume>22</volume><issue>28</issue><spage>1631</spage><epage>16313</epage><pages>1631-16313</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
. Simulations were conducted using different density functional theory methods (PBE, BLYP and revPBE), with and without the inclusion of dispersion interactions (-D3). Analysis of the ion-water structure and interaction strength, water exchange between the first and second hydration shell, and hydrogen bond network and low-frequency reorientation dynamics around the metal ions have been used to characterise the influence of solution composition on the ionic solvation shell. Counterions affect the properties of the hydration shell not only when they are directly coordinated to the metal ion, but also when they are at the second coordination shell. Chloride ions reduce the sodium hydration shell and expand the calcium hydration shell by stabilizing under-coordinated hydrated Na(H
2
O)
5
+
complexes and over-coordinated Ca(H
2
O)
7
2+
. The same behaviour is observed in CaSO
4
(aq), where Ca
2+
and SO
4
2−
form almost exclusively solvent-shared ion pairs. Water exchange between the first and second hydration shell around Ca
2+
in CaSO
4
(aq) is drastically decelerated compared with the simulations of the hydrated metal ion (single Ca
2+
, no counterions). Velocity autocorrelation function analysis, used to probe the strength of the local ion-water interaction, shows a smoother decay of Mg
2+
in MgCl
2
(aq), which is a clear indication of a looser inter-hexahedral vibration in the presence of chloride ions located in the second coordination shell of Mg
2+
. The hydrogen bond statistics and orientational dynamics in the ionic solvation shell show that the influence on the water-water network cannot only be ascribed to the specific cation-water interaction, but also to the subtle interplay between the level of hydration of the ions, and the interactions between ions, especially those of opposite charge. As many reactive processes involving solvated metal ions occur in environments that are far from pure water but rich in ions, this computational study shows how the solution composition can result in significant differences in behaviour and function of the ionic solvation shell.
We present an
ab initio
molecular dynamics study of the alkali metal ions Li
+
, Na
+
, K
+
and Cs
+
, and of the alkaline earth metal ions Mg
2+
and Ca
2+
in both pure water and electrolyte solutions containing the counterions Cl
−
and SO
4
2−
.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0cp01957g</doi><tpages>13</tpages><orcidid>https://orcid.org/0000-0002-4485-4468</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9076 |
| ispartof | Physical chemistry chemical physics : PCCP, 2020-07, Vol.22 (28), p.1631-16313 |
| issn | 1463-9076 1463-9084 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_2423060728 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Alkali metals Alkaline earth metals Autocorrelation functions Calcium ions Chloride ions Composition effects Computer simulation Coordination Deceleration Density functional theory Function analysis Hydration Hydrogen bonds Ion pairs Ions Magnesium chloride Metal ions Molecular dynamics Simulation Sodium Solvation Time correlation functions |
| title | Density functional theory based molecular dynamics study of solution composition effects on the solvation shell of metal ions |
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