Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

Kumal, Raju R.; Wimalasiri, Pubudu N.; Servis, Michael J.; Uysal, Ahmet

doi:10.1021/acs.jpclett.2c00934

Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

Journal Article · Thu Jun 02 00:00:00 EDT 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c00934· OSTI ID:1905888

^[1]; Wimalasiri, Pubudu N. ^[1]; ^[1]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)

Anions play significant roles in the separation of lanthanides and actinides. The molecular-scale details of how these anions behave at aqueous interfaces are not well understood, especially at high ionic strengths. Here, we describe the interfacial structure of thiocyanate anions at a soft charged interface up to 5 M bulk concentration with combined classical and phase-sensitive and molecular dynamics (MD) simulations. At low concentrations thiocyanate ions are mostly oriented with their sulfur end pointing toward the charged surfactants. In this work, the VSFG signal reaches a plateau at around 100 mM bulk concentration, followed by significant changes above 1 M. At high concentrations a new thiocyanate population emerges with their sulfur end pointing toward the bulk liquid. The –CN stretch frequency is different for up and down oriented SCN^– ions, indicating different coordination environments. These results provide key molecular-level insights for the interfacial behavior of complex anions in highly concentrated solutions.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1905888

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 22 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

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