dc.contributor.author | Roberts, Sean Thomas | |
dc.contributor.author | Ramasesha, Krupa | |
dc.contributor.author | Petersen, Poul B. | |
dc.contributor.author | Mandal, Aritra | |
dc.contributor.author | Tokmakoff, Andrei | |
dc.date.accessioned | 2012-03-14T20:28:04Z | |
dc.date.available | 2012-03-14T20:28:04Z | |
dc.date.issued | 2011-02 | |
dc.date.submitted | 2011-01 | |
dc.identifier.issn | 1089-5639 | |
dc.identifier.issn | 1520-5215 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/69657 | |
dc.description.abstract | While it is generally recognized that the hydroxide ion can rapidly diffuse through aqueous solution due to its ability to accept a proton from a neighboring water molecule, a description of the OH− solvation structure and mechanism of proton transfer to the ion remains controversial. In this report, we present the results of femtosecond infrared spectroscopy measurements of the O−H stretching transition of dilute HOD dissolved in NaOD/D2O. Pump−probe, photon echo peak shift, and two-dimensional infrared spectroscopy experiments performed as a function of deuteroxide concentration are used to assign spectral signatures that arise from the OH− ion and its solvation shell. A spectral feature that decays on a 110 fs time scale is assigned to the relaxation of transiently formed configurations wherein a proton is equally shared between a HOD molecule and an OD− ion. Over picosecond waiting times, features appear in 2D IR spectra that are indicative of the exchange of population between OH− ions and HOD molecules due to deuteron transfer. The construction of a spectral model that includes spectral relaxation, chemical exchange, and thermalization processes, and self-consistently treats all of our data, allows us to qualitatively explain the results of our experiments and gives a lower bound of 3 ps for the deuteron transfer kinetics. | en_US |
dc.description.sponsorship | United States. Dept. of Energy (Contract No. DE-FG02-99ER14988) | en_US |
dc.description.sponsorship | American Chemical Society (Petroleum Research Fund) | en_US |
dc.description.sponsorship | Henry & Camille Dreyfus Foundation | en_US |
dc.description.sponsorship | Carlsberg Foundation | en_US |
dc.language.iso | en_US | |
dc.publisher | American Chemical Society | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1021/jp108474p | en_US |
dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | en_US |
dc.source | Prof. Tokmakoff via Erja Kajosalo | en_US |
dc.title | Proton Transfer in Concentrated Aqueous Hydroxide Visualized using Ultrafast Infrared Spectroscopy | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Roberts, Sean T. et al. “Proton Transfer in Concentrated Aqueous Hydroxide Visualized Using Ultrafast Infrared Spectroscopy.” The Journal of Physical Chemistry A 115.16 (2011): 3957–3972. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.approver | Tokmakoff, Andrei | |
dc.contributor.mitauthor | Tokmakoff, Andrei | |
dc.contributor.mitauthor | Roberts, Sean Thomas | |
dc.contributor.mitauthor | Ramasesha, Krupa | |
dc.contributor.mitauthor | Petersen, Poul B. | |
dc.contributor.mitauthor | Mandal, Aritra | |
dc.relation.journal | Journal of Physical Chemistry A | en_US |
dc.eprint.version | Author's final manuscript | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Roberts, Sean T.; Ramasesha, Krupa; Petersen, Poul B.; Mandal, Aritra; Tokmakoff, Andrei | en |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |