Escape of anions from geminate recombination in THF due to charge delocalization
Geminate recombination of 24 radical anions (M&z.rad; − ) with solvated protons (RH 2 + ) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad; − and RH 2 + together to form intimate (contact and solvent separated) ion pairs, d...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2017-12, Vol.19 (48), p.32272-32285 |
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| creator | Chen, Hung-Cheng Cook, Andrew R Asaoka, Sadayuki Boschen, Jeffery S Windus, Theresa L Miller, John R |
| description | Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad;
−
and RH
2
+
together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH
2
+
to M&z.rad;
−
. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast ( |
| doi_str_mv | 10.1039/c7cp05880b |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmed_primary_29192921</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2010851190</sourcerecordid><originalsourceid>FETCH-LOGICAL-c400t-fc0e3816f4869fb56822a752a635334c70f33f75ff2ae233ffeb095af792ee8c3</originalsourceid><addsrcrecordid>eNpd0cFLHTEQBvBQKtXaXrxbgl6k8Owk2WySoz60CoIe7Dlk5010ZXfzmuwe6l_f1aev0FM-mB8Dk4-xAwGnApT7gQbXoK2F5gPbE1WtFg5s9XGbTb3LPpfyBABCC_WJ7UonnHRS7LG7i4JhTTxFHoY2DYXHnHr-QH07hJF4Jkx985LnIW8Hfn91yVcT8TFxfAz5gfiKuoSha59fzRe2E0NX6Ovbu89-XV7cL68WN7c_r5dnNwusAMZFRCBlRR0rW7vY6NpKGYyWoVZaqQoNRKWi0THKQHKOkRpwOkTjJJFFtc-ONntTGVtfsB0JHzENA-HoRSWksWJGJxu0zun3RGX0fVuQui4MlKbihTOi1hLAzfT4P_qUpjzMJ3gJAqwWwsGsvm8U5lRKpujXue1D_uMF-Jcy_NIs717LOJ_xt7eVU9PTakvff38GhxuQC26n_9pUfwGZRYxO</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2010851190</pqid></control><display><type>article</type><title>Escape of anions from geminate recombination in THF due to charge delocalization</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Chen, Hung-Cheng ; Cook, Andrew R ; Asaoka, Sadayuki ; Boschen, Jeffery S ; Windus, Theresa L ; Miller, John R</creator><creatorcontrib>Chen, Hung-Cheng ; Cook, Andrew R ; Asaoka, Sadayuki ; Boschen, Jeffery S ; Windus, Theresa L ; Miller, John R ; Ames Laboratory (AMES), Ames, IA (United States) ; Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><description><![CDATA[Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad;
−
and RH
2
+
together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH
2
+
to M&z.rad;
−
. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (<0.2 ns) to measure, except for the anion of TCNE which did not undergo proton transfer. PT to C atoms was as slow as 70 ns and was always slow enough to be observable. A possible effect of charge delocalization on the PT rates could not be clearly separated from other factors. For 21 of the 24 molecules studied here, a free ion yield (71.6 ± 6.2 nmol J
−1
) comprising ∼29% of the total, was formed. This yield of "Type I" free ions is independent of the PT rate because it arises entirely by escape from the initial distribution of ion pair distances without forming intimate ion pairs. Three anions of oligo(9,9-dihexyl)fluorenes, F
n
&z.rad;
−
(
n
= 2-4) were able to escape from intimate ion-pairs to form additional yields of "Type II" free ions with escape rate constants near 3 × 10
6
s
−1
. These experiments find no evidence for an inverted region for proton transfer.
Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis.]]></description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/c7cp05880b</identifier><identifier>PMID: 29192921</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Anions ; charge delocalization ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; ion pair ; Ion pairs ; ion recombination ; Ions ; oligofluorenes ; Onsager escape ; Protons ; pulse radiolysis ; radiation chemistry ; Radiolysis ; Rate constants ; Tetrahydrofuran</subject><ispartof>Physical chemistry chemical physics : PCCP, 2017-12, Vol.19 (48), p.32272-32285</ispartof><rights>Copyright Royal Society of Chemistry 2017</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c400t-fc0e3816f4869fb56822a752a635334c70f33f75ff2ae233ffeb095af792ee8c3</citedby><cites>FETCH-LOGICAL-c400t-fc0e3816f4869fb56822a752a635334c70f33f75ff2ae233ffeb095af792ee8c3</cites><orcidid>0000-0001-6633-3447 ; 0000-0003-4377-7445 ; 0000000343777445 ; 0000000166333447</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29192921$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/servlets/purl/1412781$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Chen, Hung-Cheng</creatorcontrib><creatorcontrib>Cook, Andrew R</creatorcontrib><creatorcontrib>Asaoka, Sadayuki</creatorcontrib><creatorcontrib>Boschen, Jeffery S</creatorcontrib><creatorcontrib>Windus, Theresa L</creatorcontrib><creatorcontrib>Miller, John R</creatorcontrib><creatorcontrib>Ames Laboratory (AMES), Ames, IA (United States)</creatorcontrib><creatorcontrib>Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><title>Escape of anions from geminate recombination in THF due to charge delocalization</title><title>Physical chemistry chemical physics : PCCP</title><addtitle>Phys Chem Chem Phys</addtitle><description><![CDATA[Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad;
−
and RH
2
+
together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH
2
+
to M&z.rad;
−
. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (<0.2 ns) to measure, except for the anion of TCNE which did not undergo proton transfer. PT to C atoms was as slow as 70 ns and was always slow enough to be observable. A possible effect of charge delocalization on the PT rates could not be clearly separated from other factors. For 21 of the 24 molecules studied here, a free ion yield (71.6 ± 6.2 nmol J
−1
) comprising ∼29% of the total, was formed. This yield of "Type I" free ions is independent of the PT rate because it arises entirely by escape from the initial distribution of ion pair distances without forming intimate ion pairs. Three anions of oligo(9,9-dihexyl)fluorenes, F
n
&z.rad;
−
(
n
= 2-4) were able to escape from intimate ion-pairs to form additional yields of "Type II" free ions with escape rate constants near 3 × 10
6
s
−1
. These experiments find no evidence for an inverted region for proton transfer.
Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis.]]></description><subject>Anions</subject><subject>charge delocalization</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>ion pair</subject><subject>Ion pairs</subject><subject>ion recombination</subject><subject>Ions</subject><subject>oligofluorenes</subject><subject>Onsager escape</subject><subject>Protons</subject><subject>pulse radiolysis</subject><subject>radiation chemistry</subject><subject>Radiolysis</subject><subject>Rate constants</subject><subject>Tetrahydrofuran</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNpd0cFLHTEQBvBQKtXaXrxbgl6k8Owk2WySoz60CoIe7Dlk5010ZXfzmuwe6l_f1aev0FM-mB8Dk4-xAwGnApT7gQbXoK2F5gPbE1WtFg5s9XGbTb3LPpfyBABCC_WJ7UonnHRS7LG7i4JhTTxFHoY2DYXHnHr-QH07hJF4Jkx985LnIW8Hfn91yVcT8TFxfAz5gfiKuoSha59fzRe2E0NX6Ovbu89-XV7cL68WN7c_r5dnNwusAMZFRCBlRR0rW7vY6NpKGYyWoVZaqQoNRKWi0THKQHKOkRpwOkTjJJFFtc-ONntTGVtfsB0JHzENA-HoRSWksWJGJxu0zun3RGX0fVuQui4MlKbihTOi1hLAzfT4P_qUpjzMJ3gJAqwWwsGsvm8U5lRKpujXue1D_uMF-Jcy_NIs717LOJ_xt7eVU9PTakvff38GhxuQC26n_9pUfwGZRYxO</recordid><startdate>20171213</startdate><enddate>20171213</enddate><creator>Chen, Hung-Cheng</creator><creator>Cook, Andrew R</creator><creator>Asaoka, Sadayuki</creator><creator>Boschen, Jeffery S</creator><creator>Windus, Theresa L</creator><creator>Miller, John R</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><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><scope>OIOZB</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0001-6633-3447</orcidid><orcidid>https://orcid.org/0000-0003-4377-7445</orcidid><orcidid>https://orcid.org/0000000343777445</orcidid><orcidid>https://orcid.org/0000000166333447</orcidid></search><sort><creationdate>20171213</creationdate><title>Escape of anions from geminate recombination in THF due to charge delocalization</title><author>Chen, Hung-Cheng ; Cook, Andrew R ; Asaoka, Sadayuki ; Boschen, Jeffery S ; Windus, Theresa L ; Miller, John R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c400t-fc0e3816f4869fb56822a752a635334c70f33f75ff2ae233ffeb095af792ee8c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Anions</topic><topic>charge delocalization</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>ion pair</topic><topic>Ion pairs</topic><topic>ion recombination</topic><topic>Ions</topic><topic>oligofluorenes</topic><topic>Onsager escape</topic><topic>Protons</topic><topic>pulse radiolysis</topic><topic>radiation chemistry</topic><topic>Radiolysis</topic><topic>Rate constants</topic><topic>Tetrahydrofuran</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Chen, Hung-Cheng</creatorcontrib><creatorcontrib>Cook, Andrew R</creatorcontrib><creatorcontrib>Asaoka, Sadayuki</creatorcontrib><creatorcontrib>Boschen, Jeffery S</creatorcontrib><creatorcontrib>Windus, Theresa L</creatorcontrib><creatorcontrib>Miller, John R</creatorcontrib><creatorcontrib>Ames Laboratory (AMES), Ames, IA (United States)</creatorcontrib><creatorcontrib>Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><collection>PubMed</collection><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><collection>OSTI.GOV - Hybrid</collection><collection>OSTI.GOV</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Chen, Hung-Cheng</au><au>Cook, Andrew R</au><au>Asaoka, Sadayuki</au><au>Boschen, Jeffery S</au><au>Windus, Theresa L</au><au>Miller, John R</au><aucorp>Ames Laboratory (AMES), Ames, IA (United States)</aucorp><aucorp>Brookhaven National Laboratory (BNL), Upton, NY (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Escape of anions from geminate recombination in THF due to charge delocalization</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><addtitle>Phys Chem Chem Phys</addtitle><date>2017-12-13</date><risdate>2017</risdate><volume>19</volume><issue>48</issue><spage>32272</spage><epage>32285</epage><pages>32272-32285</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract><![CDATA[Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis. The recombination has two steps: (1) diffusion of M&z.rad;
−
and RH
2
+
together to form intimate (contact and solvent separated) ion pairs, driven by Coulomb attraction; (2) annihilation of anions due to proton transfer (PT) from RH
2
+
to M&z.rad;
−
. The non-exponential time-dependence of the geminate diffusion was determined. For all molecules protonated on O or N atoms the subsequent PT step is too fast (<0.2 ns) to measure, except for the anion of TCNE which did not undergo proton transfer. PT to C atoms was as slow as 70 ns and was always slow enough to be observable. A possible effect of charge delocalization on the PT rates could not be clearly separated from other factors. For 21 of the 24 molecules studied here, a free ion yield (71.6 ± 6.2 nmol J
−1
) comprising ∼29% of the total, was formed. This yield of "Type I" free ions is independent of the PT rate because it arises entirely by escape from the initial distribution of ion pair distances without forming intimate ion pairs. Three anions of oligo(9,9-dihexyl)fluorenes, F
n
&z.rad;
−
(
n
= 2-4) were able to escape from intimate ion-pairs to form additional yields of "Type II" free ions with escape rate constants near 3 × 10
6
s
−1
. These experiments find no evidence for an inverted region for proton transfer.
Geminate recombination of 24 radical anions (M&z.rad;
−
) with solvated protons (RH
2
+
) was studied in tetrahydrofuran (THF) with pulse radiolysis.]]></abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>29192921</pmid><doi>10.1039/c7cp05880b</doi><tpages>14</tpages><orcidid>https://orcid.org/0000-0001-6633-3447</orcidid><orcidid>https://orcid.org/0000-0003-4377-7445</orcidid><orcidid>https://orcid.org/0000000343777445</orcidid><orcidid>https://orcid.org/0000000166333447</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9076 |
| ispartof | Physical chemistry chemical physics : PCCP, 2017-12, Vol.19 (48), p.32272-32285 |
| issn | 1463-9076 1463-9084 |
| language | eng |
| recordid | cdi_pubmed_primary_29192921 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Anions charge delocalization INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ion pair Ion pairs ion recombination Ions oligofluorenes Onsager escape Protons pulse radiolysis radiation chemistry Radiolysis Rate constants Tetrahydrofuran |
| title | Escape of anions from geminate recombination in THF due to charge delocalization |
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