Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

Suarez, Sophia N.; Wishart, James F.; Rua, Armando; Cuffari, David; Pilar, Kartik; Hatcher, Jasmine L.; Ramati, Sharon

doi:10.1021/acs.jpcb.5b08658

Do TFSA anions slither? Pressure exposes the role of TFSA conformational exchange in self-diffusion

Journal Article · Wed Oct 28 00:00:00 EDT 2015 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.5b08658· OSTI ID:1222605

Suarez, Sophia N. ^[1]; Wishart, James F. ^[2]; Rua, Armando ^[3]; Cuffari, David ^[1]; Pilar, Kartik ^[3]; Hatcher, Jasmine L. ^[4]; Ramati, Sharon ^[2]

Brooklyn College, Brooklyn, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Hunter College, New York, NY (United States)
City Univ. Graduate School (CUNY), NY, New York (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

Multi-nuclear (¹H, ²H, and ¹⁹F) magnetic resonance spectroscopy techniques as functions of temperature and pressure were applied to the study of selectively deuterated 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMIM TFSA) ionic liquid isotopologues and related ionic liquids. For EMIM TFSA, temperature-dependent ²H T₁ data indicate stronger electric field gradients in the alkyl chain region compared to the imidazolium ring. Most significantly, the pressure dependences of the EMIM and TFSA self-diffusion coefficients revealed that the displacements of the cations and anions are independent, with diffusion of the TFSA anions being slowed much more by increasing pressure than for the EMIM cations, as shown by their respective activation volumes (28.8 ± 2.5 cm³/mol for TFSA vs. 14.6 ± 1.3 cm³/mol for EMIM). Increasing pressure may lower the mobility of the TFSA anion by hindering its interconversion between trans and cis conformers, a process that is coupled to diffusion according to published molecular dynamics simulations. Measured activation volumes (ΔV^‡) for ion self-diffusion in EMIM bis(fluoromethylsulfonyl)amide and EMIM tetrafluoroborate support this hypothesis.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1222605

Alternate ID(s):: OSTI ID: 1226072

Report Number(s):: BNL--108392-2015-JA; BNL--108556-2015-JA; KC0301010

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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