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Data from: Molecular-level Origin of the Carboxylate Head Group Response to Divalent Metal Ion Complexation at the Air-water Interface
Johnson, Mark A
Denton, Joanna K
Date Created and/or Issued
Time period of project: 2016-09-13 to 2018-01-28
Contributing Institution
UC San Diego, Research Data Curation Program
Center for Aerosol Impacts on Chemistry of the Environment (CAICE)
Rights Information
Under copyright
Constraint(s) on Use: This work is protected by the U.S. Copyright Law (Title 17, U.S.C.). Use of this work beyond that allowed by "fair use" or any license applied to this work requires written permission of the copyright holder(s). Responsibility for obtaining permissions and any use and distribution of this work rests exclusively with the user and not the UC San Diego Library. Inquiries can be made to the UC San Diego Library program having custody of the work.
Use: This work is available from the UC San Diego Library. This digital copy of the work is intended to support research, teaching, and private study.
Rights Holder and Contact
UC Regents
Publication abstract: We exploit gas-phase cluster ion techniques to provide insight into the local interactions underlying divalent metal ion-driven changes in the spectra of carboxylic acids at the air-water interface. This information is used to clarify the experimental findings that the CO stretching bands of long chain acids appear at very similar energies when the head group is deprotonated by high sub-phase pH or is exposed to relatively high concentrations of Ca2+ metal ions. To this end, we report the evolution of the vibrational spectra of size-selected [Ca2+·RCO2¯]+·(H2O)n=0-12 and RCO2¯·(H2O)n=0-14 cluster ions toward the features observed at the air-water interface. Surprisingly, not only does stepwise hydration of the RCO2¯ anion and the [Ca2+·RCO2¯]+ contact ion pair yield solvatochromic responses in opposite directions, but in both cases, the responses of the two (symmetric and asymmetric stretching) CO bands to hydration are opposite to each other. The result is that the two CO bands evolve toward their interfacial asymptotes from opposite directions. Simulations of the [Ca2+·RCO2¯]+·(H2O)n clusters indicate that the metal ion remains directly bound to the head group in a contact ion pair motif as the asymmetric CO stretch converges at the interfacial value by n = 12. This establishes that direct metal complexation or deprotonation can account for the interfacial behavior. We discuss these effects in the context of a model that invokes the water network-dependent local electric field along the C-C bond that connects the head group to the hydrocarbon tail as the key parameter that is correlated with the observed trends.
Research Data Curation Program, UC San Diego, La Jolla, 92093-0175 (
Denton, Joanna K.; Kelleher, Patrick J.; Baer, Marcel D.; Kathmann, Shawn M.; Mundy, Christopher J.; Wellen Rudd, Bethany A. ; Allen, Heather C.; Choi, Tae Hoon; Jordan, Kenneth D.; Johnson, Mark A. (2019). Data from: Molecular-level Origin of the Carboxylate Head Group Response to Divalent Metal Ion Complexation at the Air-water Interface. In Center for Aerosol Impacts on Chemistry of the Environment (CAICE). UC San Diego Library Digital Collections.
Joanna K. Denton, Patrick J. Kelleher, Mark A. Johnson, Marcel D. Baer, Shawn M. Kathmann, Christopher J. Mundy, Bethany A. Wellen Rudd, Heather C. Allen, Tae Hoon Choi, and Kenneth D. Jordan. 2019. Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface. Proceedings of the National Academy of Sciences Jul 2019, 201818600;
No linguistic content; Not applicable
Metal complex

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