TY - JOUR
T1 - Morphology and intermolecular dynamics of 1-Alkyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ionic liquids
T2 - Structural and dynamic evidence of nanoscale segregation
AU - Russina, Olga
AU - Triolo, Alessandro
AU - Gontrani, Lorenzo
AU - Caminiti, Ruggero
AU - Xiao, Dong
AU - Hines, Larry G.
AU - Bartsch, Richard A.
AU - Quitevis, Edward L.
AU - Plechkova, Natalia
AU - Seddon, Kenneth R.
PY - 2009/10/21
Y1 - 2009/10/21
N2 - Here we report on the structural and dynamical properties of a series of room temperature ionic liquids, namely 1-Alkyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ([Cnmim][NTf2]), with varying alkyl chain lengths (1≤n≤10) at ambient temperature, where all the salts are stable liquids. Using small-wide angle x-ray scattering (SWAXS), three major diffraction peaks are found: two high- Q peaks that show little dependence on the alkyl chain length (n) and a low-Q peak that strongly depends both in amplitude and position on n. This low-Q peak is the signature of the occurrence of nanoscale structural heterogeneities whose sizes depend on the length of the alkyl chain and are related to chain segregation into nano-domains. Using optical heterodyne-detected Raman-induced Kerr effect spectroscopy, we access intermolecular dynamic features that suggest that chain aggregation only occurs for n≥3, in agreement with the SWAXS data. Moreover, the increase in the frequency and width of the main band of the optical Kerr effect spectra in going from n = 2 to 3 is consistent with stiffening of the intermolecular potential due to chain segregation. Multicomponent line shape analysis suggests that there are least three modes that underlie the main band in the 0-200 cm-1 region of the optical Kerr effect spectra of these ionic liquids. Given the similarity of ionic liquids to other complex fluid systems, we assign the low-frequency component to a fast β-relaxation mode and the intermediate- and high-frequency components to librational modes.
AB - Here we report on the structural and dynamical properties of a series of room temperature ionic liquids, namely 1-Alkyl-3-methylimidazolium bis{(trifluoromethane)sulfonyl}amide ([Cnmim][NTf2]), with varying alkyl chain lengths (1≤n≤10) at ambient temperature, where all the salts are stable liquids. Using small-wide angle x-ray scattering (SWAXS), three major diffraction peaks are found: two high- Q peaks that show little dependence on the alkyl chain length (n) and a low-Q peak that strongly depends both in amplitude and position on n. This low-Q peak is the signature of the occurrence of nanoscale structural heterogeneities whose sizes depend on the length of the alkyl chain and are related to chain segregation into nano-domains. Using optical heterodyne-detected Raman-induced Kerr effect spectroscopy, we access intermolecular dynamic features that suggest that chain aggregation only occurs for n≥3, in agreement with the SWAXS data. Moreover, the increase in the frequency and width of the main band of the optical Kerr effect spectra in going from n = 2 to 3 is consistent with stiffening of the intermolecular potential due to chain segregation. Multicomponent line shape analysis suggests that there are least three modes that underlie the main band in the 0-200 cm-1 region of the optical Kerr effect spectra of these ionic liquids. Given the similarity of ionic liquids to other complex fluid systems, we assign the low-frequency component to a fast β-relaxation mode and the intermediate- and high-frequency components to librational modes.
UR - http://www.scopus.com/inward/record.url?scp=84881660311&partnerID=8YFLogxK
U2 - 10.1088/0953-8984/21/42/424121
DO - 10.1088/0953-8984/21/42/424121
M3 - Article
AN - SCOPUS:84881660311
VL - 21
JO - Journal of Physics Condensed Matter
JF - Journal of Physics Condensed Matter
SN - 0953-8984
IS - 42
M1 - 424121
ER -