Complexation dynamics of CH3SCN and Li+ in acetonitrile studied by two-dimensional infrared spectroscopy
DC Field | Value | Language |
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dc.contributor.author | Kwon, YoungAh | - |
dc.contributor.author | Park, Sungnam | - |
dc.date.accessioned | 2021-09-05T01:15:40Z | - |
dc.date.available | 2021-09-05T01:15:40Z | - |
dc.date.created | 2021-06-15 | - |
dc.date.issued | 2015 | - |
dc.identifier.issn | 1463-9076 | - |
dc.identifier.uri | https://scholar.korea.ac.kr/handle/2021.sw.korea/96350 | - |
dc.description.abstract | Ion-molecule complexation dynamics were studied with CH3SCN and Li+ in acetonitrile by vibrationally probing the nitrile stretching vibration of CH3SCN. The nitrile stretching vibration of CH3SCN has a long lifetime (T-1 = similar to 90 ps) and its frequency is significantly blue-shifted when CH3SCN is bound with Li+ ions to form a CH3SCN center dot center dot center dot Li+ complex in acetonitrile. Such spectral properties enable us to distinguish free CH3SCN and the CH3SCN center dot center dot center dot Li+ complex in solutions and measure their dynamics occurring on hundred picosecond timescales. For the complexation between CH3SCN and Li+ in acetonitrile, the change in enthalpy (Delta H = -7.17 kJ mol(-1)) and the change in entropy (Delta S = -34.4 J K-1 mol(-1)) were determined by temperature-dependent FTIR experiments. Polarization-controlled infrared pump-probe (IR PP) spectroscopy was used to measure the population decay and orientational dynamics of free CH3SCN and the CH3SCN center dot center dot center dot Li+ complex. Especially, the orientational relaxation of the CH3SCN center dot center dot center dot Li+ complex was found to be almost 3 times slower than those of free CH3SCN because Li+ ions strongly interact with the neighboring solvents. Most importantly, the complexation dynamics of CH3SCN and Li+ in acetonitrile were successfully measured in real time by 2DIR spectroscopy for the first time and the dissociation and association time constants were directly determined by using the two-species exchange kinetic model. Our experimental results provide a comprehensive overview of the ion-molecule complexation dynamics in solutions occurring under thermal equilibrium conditions. | - |
dc.language | English | - |
dc.language.iso | en | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.subject | HYDROGEN-BOND EXCHANGE | - |
dc.subject | 2D IR SPECTROSCOPY | - |
dc.subject | ULTRAFAST DYNAMICS | - |
dc.subject | CATHODE MATERIAL | - |
dc.subject | ION-PAIRS | - |
dc.subject | WATER | - |
dc.subject | EQUILIBRIUM | - |
dc.subject | HYDRATION | - |
dc.subject | PEPTIDES | - |
dc.subject | PROBES | - |
dc.title | Complexation dynamics of CH3SCN and Li+ in acetonitrile studied by two-dimensional infrared spectroscopy | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Park, Sungnam | - |
dc.identifier.doi | 10.1039/c5cp02833g | - |
dc.identifier.scopusid | 2-s2.0-84941902976 | - |
dc.identifier.wosid | 000361543200056 | - |
dc.identifier.bibliographicCitation | PHYSICAL CHEMISTRY CHEMICAL PHYSICS, v.17, no.37, pp.24193 - 24200 | - |
dc.relation.isPartOf | PHYSICAL CHEMISTRY CHEMICAL PHYSICS | - |
dc.citation.title | PHYSICAL CHEMISTRY CHEMICAL PHYSICS | - |
dc.citation.volume | 17 | - |
dc.citation.number | 37 | - |
dc.citation.startPage | 24193 | - |
dc.citation.endPage | 24200 | - |
dc.type.rims | ART | - |
dc.type.docType | Article | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalResearchArea | Physics | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical | - |
dc.relation.journalWebOfScienceCategory | Physics, Atomic, Molecular & Chemical | - |
dc.subject.keywordPlus | HYDROGEN-BOND EXCHANGE | - |
dc.subject.keywordPlus | 2D IR SPECTROSCOPY | - |
dc.subject.keywordPlus | ULTRAFAST DYNAMICS | - |
dc.subject.keywordPlus | CATHODE MATERIAL | - |
dc.subject.keywordPlus | ION-PAIRS | - |
dc.subject.keywordPlus | WATER | - |
dc.subject.keywordPlus | EQUILIBRIUM | - |
dc.subject.keywordPlus | HYDRATION | - |
dc.subject.keywordPlus | PEPTIDES | - |
dc.subject.keywordPlus | PROBES | - |
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