Vibrational relaxation and microsolvation of DF after F-atom reactions in polar solvents
Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to...
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| Veröffentlicht in: | Science (American Association for the Advancement of Science) 2015-01, Vol.347 (6221), p.530-533 |
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| creator | Dunning, G. T. Glowacki, D. R. Preston, T. J. Greaves, S. J. Greetham, G. M. Clark, I. P. Towrie, M. Harvey, J. N. Orr-Ewing, A. J. |
| description | Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to vibrational motion of the deuterium fluoride (DF) product that competes with dissipation of the energy to the solvent bath, despite strong solvent coupling. Transient infrared absorption spectroscopy and molecular dynamics simulations show that after DF forms its first hydrogen bond on a subpicosecond time scale, DF vibrational relaxation and further solvent restructuring occur over more than 10 picoseconds. Characteristic dynamics of gas-phase F-atom reactions with hydrogen-containing molecules persist in polar organic solvents, and the spectral evolution of the DF products serves as a probe of solvent reorganization induced by a chemical reaction. |
| doi_str_mv | 10.1126/science.aaa0103 |
| format | Article |
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T. ; Glowacki, D. R. ; Preston, T. J. ; Greaves, S. J. ; Greetham, G. M. ; Clark, I. P. ; Towrie, M. ; Harvey, J. N. ; Orr-Ewing, A. J.</creator><creatorcontrib>Dunning, G. T. ; Glowacki, D. R. ; Preston, T. J. ; Greaves, S. J. ; Greetham, G. M. ; Clark, I. P. ; Towrie, M. ; Harvey, J. N. ; Orr-Ewing, A. J.</creatorcontrib><description>Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to vibrational motion of the deuterium fluoride (DF) product that competes with dissipation of the energy to the solvent bath, despite strong solvent coupling. Transient infrared absorption spectroscopy and molecular dynamics simulations show that after DF forms its first hydrogen bond on a subpicosecond time scale, DF vibrational relaxation and further solvent restructuring occur over more than 10 picoseconds. Characteristic dynamics of gas-phase F-atom reactions with hydrogen-containing molecules persist in polar organic solvents, and the spectral evolution of the DF products serves as a probe of solvent reorganization induced by a chemical reaction.</description><identifier>ISSN: 0036-8075</identifier><identifier>EISSN: 1095-9203</identifier><identifier>DOI: 10.1126/science.aaa0103</identifier><identifier>CODEN: SCIEAS</identifier><language>eng</language><publisher>Washington: American Association for the Advancement of Science</publisher><subject>Atoms & subatomic particles ; Chemical reactions ; Chemistry ; Deuterium fluorides ; Dissipation ; Dynamics ; Gas phases ; Infrared absorption ; Inhalants ; Organic Chemistry ; Solution chemistry ; Solvents ; Spectroscopy ; Vibration</subject><ispartof>Science (American Association for the Advancement of Science), 2015-01, Vol.347 (6221), p.530-533</ispartof><rights>Copyright © 2015 American Association for the Advancement of Science</rights><rights>Copyright © 2015, American Association for the Advancement of Science</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c365t-f6d86c9f993444887f8d6873c9235850e606e6ab1e82b1daecf9c11ade9c21ce3</citedby><cites>FETCH-LOGICAL-c365t-f6d86c9f993444887f8d6873c9235850e606e6ab1e82b1daecf9c11ade9c21ce3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.jstor.org/stable/pdf/24745788$$EPDF$$P50$$Gjstor$$H</linktopdf><linktohtml>$$Uhttps://www.jstor.org/stable/24745788$$EHTML$$P50$$Gjstor$$H</linktohtml><link.rule.ids>314,776,780,799,2871,2872,27901,27902,57992,58225</link.rule.ids></links><search><creatorcontrib>Dunning, G. 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| source | Jstor Complete Legacy; Science Magazine |
| subjects | Atoms & subatomic particles Chemical reactions Chemistry Deuterium fluorides Dissipation Dynamics Gas phases Infrared absorption Inhalants Organic Chemistry Solution chemistry Solvents Spectroscopy Vibration |
| title | Vibrational relaxation and microsolvation of DF after F-atom reactions in polar solvents |
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