Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Choi, Jun-Ho | - |
dc.contributor.author | Kim, Heejae | - |
dc.contributor.author | Kim, Seongheun | - |
dc.contributor.author | Lim, Sohee | - |
dc.contributor.author | Chon, Bonghwan | - |
dc.contributor.author | Cho, Minhaeng | - |
dc.date.accessioned | 2021-09-04T15:59:18Z | - |
dc.date.available | 2021-09-04T15:59:18Z | - |
dc.date.created | 2021-06-18 | - |
dc.date.issued | 2015-05-28 | - |
dc.identifier.issn | 0021-9606 | - |
dc.identifier.uri | https://scholar.korea.ac.kr/handle/2021.sw.korea/93517 | - |
dc.description.abstract | The vibrational frequency, frequency fluctuation dynamics, and transition dipole moment of the O-D stretch mode of HDO molecule in aqueous solutions are strongly dependent on its local electrostatic environment and hydrogen-bond network structure. Therefore, the time-resolved vibrational spectroscopy the O-D stretch mode has been particularly used to investigate specific ion effects on water structure. Despite prolonged efforts to understand the interplay of O-D vibrational dynamics with local water hydrogen-bond network and ion aggregate structures in high salt solutions, still there exists a gap between theory and experiment due to a lack of quantitative model for accurately describing O-D stretch frequency in high salt solutions. To fill this gap, we have performed numerical simulations of Raman scattering and IR absorption spectra of the O-D stretch mode of HDO in highly concentrated NaCl and KSCN solutions and compared them with experimental results. Carrying out extensive quantum chemistry calculations on not only water clusters but also ion-water clusters, we first developed a distributed vibrational solvatochromic charge model for the O-D stretch mode in aqueous salt solutions. Furthermore, the non-Condon effect on the vibrational transition dipole moment of the O-D stretch mode was fully taken into consideration with the charge response kernel that is non-local polarizability density. From the fluctuating O-D stretch mode frequencies and transition dipole vectors obtained from the molecular dynamics simulations, the O-D stretch Raman scattering and IR absorption spectra of HDO in salt solutions could be calculated. The polarization effect on the transition dipole vector of the O-D stretch mode is shown to be important and the asymmetric line shapes of the O-D stretch Raman scattering and IR absorption spectra of HDO especially in highly concentrated NaCl and KSCN solutions are in quantitative agreement with experimental results. We anticipate that this computational approach will be of critical use in interpreting linear and nonlinear vibrational spectroscopies of HDO molecule that is considered as an excellent local probe for monitoring local electrostatic and hydrogen-bonding environment in not just salt but also other confined and crowded solutions. (C) 2015 AIP Publishing LLC. | - |
dc.language | English | - |
dc.language.iso | en | - |
dc.publisher | AMER INST PHYSICS | - |
dc.subject | ULTRAFAST INFRARED-SPECTROSCOPY | - |
dc.subject | HYDROGEN-BOND DYNAMICS | - |
dc.subject | DILUTE HOD | - |
dc.subject | LIQUID WATER | - |
dc.subject | DIPOLE-MOMENT | - |
dc.subject | AB-INITIO | - |
dc.subject | RAMAN | - |
dc.subject | SIMULATIONS | - |
dc.subject | SOLVATION | - |
dc.subject | H2O | - |
dc.title | Ion aggregation in high salt solutions. III. Computational vibrational spectroscopy of HDO in aqueous salt solutions | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Choi, Jun-Ho | - |
dc.contributor.affiliatedAuthor | Cho, Minhaeng | - |
dc.identifier.doi | 10.1063/1.4920972 | - |
dc.identifier.scopusid | 2-s2.0-84930074877 | - |
dc.identifier.wosid | 000355919300002 | - |
dc.identifier.bibliographicCitation | JOURNAL OF CHEMICAL PHYSICS, v.142, no.20 | - |
dc.relation.isPartOf | JOURNAL OF CHEMICAL PHYSICS | - |
dc.citation.title | JOURNAL OF CHEMICAL PHYSICS | - |
dc.citation.volume | 142 | - |
dc.citation.number | 20 | - |
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 | ULTRAFAST INFRARED-SPECTROSCOPY | - |
dc.subject.keywordPlus | HYDROGEN-BOND DYNAMICS | - |
dc.subject.keywordPlus | DILUTE HOD | - |
dc.subject.keywordPlus | LIQUID WATER | - |
dc.subject.keywordPlus | DIPOLE-MOMENT | - |
dc.subject.keywordPlus | AB-INITIO | - |
dc.subject.keywordPlus | RAMAN | - |
dc.subject.keywordPlus | SIMULATIONS | - |
dc.subject.keywordPlus | SOLVATION | - |
dc.subject.keywordPlus | H2O | - |
Items in ScholarWorks are protected by copyright, with all rights reserved, unless otherwise indicated.
(02841) 서울특별시 성북구 안암로 14502-3290-1114
COPYRIGHT © 2021 Korea University. All Rights Reserved.
Certain data included herein are derived from the © Web of Science of Clarivate Analytics. All rights reserved.
You may not copy or re-distribute this material in whole or in part without the prior written consent of Clarivate Analytics.