The dynamics of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide room-temperature ionic liquids (RTILs) with carbon chain lengths of 2, 4, 6, and 10 were studied by measuring the orientational and spectral diffusion dynamics of the vibrational probe SeCN(-). Vibrational absorption spectra, two-dimensional infrared (2D IR), and polarization-selective pump-probe (PSPP) experiments were performed on the CN stretch. In addition, optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments were performed on the bulk liquids. The PSPP experiments yielded triexponential anisotropy decays, which were analyzed with the wobbling-in-a-cone model. The slowest decay, the complete orientational randomization, slows with increasing chain length in a hydrodynamic trend consistent with the increasing viscosity. The shortest time scale wobbling motions are insensitive to chain length, while the intermediate time scale wobbling slows mildly as the chain length increases. The 2D IR spectra measured in parallel (⟨XXXX⟩) and perpendicular (⟨XXYY⟩) polarization configurations gave different decays, showing that reorientation-induced spectral diffusion (RISD) contributes to the dynamics. The spectral diffusion caused by the RTIL structural fluctuations was obtained by removing the RISD contributions. The faster structural fluctuations are relatively insensitive to chain length. The slowest structural fluctuations slow substantially when going from Emim (2 carbon chain) to Bmim (4 carbon chain) and slow further, but more gradually, as the chain length is increased. It was shown previously that K(+) causes local ion clustering in the Emim RTIL. The K(+) effect increases with increasing chain length. The OHD-OKE measured complete structural randomization times slow substantially with increasing chain length and are much slower than the dynamics experienced by the SeCN(-) located in the ionic regions of the RTILs.
The orientational dynamics and microscopic liquid structure of a protic ionic liquid, 1-ethylimidazolium bis(trifluoromethylsulfonyl)imide (EhimNTf), and its aprotic analogue, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf), were studied at various water concentrations using optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy, linear infrared spectroscopy, and atomistic simulations. The OHD-OKE experiments essentially measure the orientational relaxation of the Ehim and Emim cations. The experiments and simulations show a significant dynamical and structural change in EhimNTf between the 2:1 ion pair:water and the 1:1 ion pair:water concentrations. The OHD-OKE data show that EmimNTf/water mixtures exhibit hydrodynamic behavior at all water concentrations up to saturation. In contrast, EhimNTf/water mixtures deviate from hydrodynamic behavior at water concentrations above 2:1. At the 1:1 concentration, the orientational randomization of the Ehim cation is slower than that predicted using viscosity data. Atomistic simulation results reveal the microscopic ionic structures of dry liquids and the preferential hydrogen bonding of water to the H atom of the N-H of Ehim over other sites on the Ehim and Emim cations. Atomistic simulation results demonstrate that in EhimNTf RTIL/water mixtures there is a substantial jump in the formation of water-water hydrogen bonds in addition to N-H-water hydrogen bonds upon increasing the water concentration from 2:1 to 1:1. Water-water hydrogen bonding strengthens the spatial coordination of the H atom of the N-H moiety of Ehim to neighboring water molecules through preferential hydrogen bonding. The jump in the concentration of water-water hydrogen bonds occurs at the Ehim/water concentration at which the orientational relaxation deviates from hydrodynamic behavior. This structural observation is confirmed with FT-IR spectra that show asymmetry in the peak for the O-D stretch that is indicative of water clusters. The formation of water clusters and the strengthening of the N-H···OH hydrogen bonds slow the orientational relaxation of Ehim cations as observed by the OHD-OKE experiments.
The isotropic phase of nematogenic liquid crystals has nanometer length scale domains with pseudonematic ordering. As the isotropic to nematic phase transition temperature (TNI) is approached from above, the orientational correlation length, ξ, of the pseudonematic domains grows as (T - T(*))(-1/2), where T(*) is 0.5-1 K below TNI. The orientational relaxation, which is a collective property of the pseudonematic domains, was measured with optical heterodyne detected-optical Kerr effect (OHD-OKE). The orientational relaxation obeys Landau-de Gennes theory, as has been shown previously. To examine the environmental evolution experienced by molecules in the pseudonematic domains, two-dimensional infrared (2D IR) vibrational echo experiments on the CN stretching mode of the non-perturbative vibrational probes 4-pentyl-4(')-selenocyanobiphenyl (5SeCB) and 4-pentyl-4(')-thiocyanobiphenyl (5SCB) in the nematogen 4-cyano-4(')-pentylbiphenyl (5CB) were performed. The 2D IR experiments measure spectral diffusion, which is caused by structural fluctuations that couple to the CN vibrational frequency. Temperature dependent studies were performed just above TNI, where the correlation length of pseudonematic domains is large and changing rapidly with temperature. These studies were compared to 2D IR experiments on 4-pentylbiphenyl (5B), a non-mesogenic liquid that is very similar in structure to 5CB. The time constants of spectral diffusion in 5CB and 5B are practically identical at temperatures ≥5 K above TNI. As the temperature is lowered, spectral diffusion in 5B slows gradually. However, the time constants for spectral diffusion in 5CB slow dramatically and diverge as T(*) is approached. This divergence has temperature dependence proportional to (T - T(*))(-1/2), precisely the same as seen for the correlation length of pseudonematic domains, but different from the observed orientational relaxation times, which are given by the Landau-de Gennes theory. The data and previous results show that spectral diffusion in 5CB has no contributions from orientational relaxation, and the structural dynamics responsible for the spectral diffusion are likely a result of density fluctuations. The results suggest that the correlation length of the density fluctuations is diverging with the same temperature dependence as the pseudonematic domain correlation length, ξ. The isotropic-nematic phase transition in liquid crystals is described in the context of the slowing of orientational relaxation associated with divergent growth of the orientational correlation length. The results presented here show that there is another divergent dynamical process, likely associated with density fluctuations.
The dynamics of the room-temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimNTf) were investigated with two-dimensional infrared (2D IR) vibrational echo spectroscopy and polarization selective pump-probe (PSPP) experiments. The CN stretch frequency of a modified Bmim cation (2-SeCN-Bmim), in which a SeCN moiety was substituted onto the C-2 position of the imidazolium ring, was used as a vibrational probe. A major result of the 2D IR experiments is the observation of a long time scale structural spectral diffusion component of 600 ps in addition to short and intermediate time scales similar to those measured for selenocyanate anion (SeCN) dissolved in BmimNTf. In contrast to 2-SeCN-Bmim, SeCN samples its inhomogeneous line width nearly an order of magnitude faster than the complete structural randomization time of neat BmimNTf liquid (870 ± 20 ps) measured with optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments. The orientational correlation function obtained from PSPP experiments on 2-SeCN-Bmim exhibits two periods of restricted angular diffusion (wobbling-in-a-cone) followed by complete orientational randomization on a time scale of 900 ± 20 ps, significantly slower than observed for SeCN but identical within experimental error to the complete structural randomization time of BmimNTf. The experiments indicate that 2-SeCN-Bmim is sensitive to local motions of the ionic region that influence the spectral diffusion and reorientation of small, anionic, and neutral molecules as well as significantly slower, longer-range fluctuations that are responsible for complete randomization of the liquid structure.
Nematogen liquids in the isotropic phase are macroscopically homogeneous but on multinanometer length scales have pseudonematic domains with correlation lengths that grow as the isotropic to nematic phase transition temperature (TNI) is approached from above. Orientational relaxation of nematogens in the isotropic phase manifests as two fast power laws and a slow exponential decay when measured by optical heterodyne detected optical Kerr effect (OHD-OKE) experiments. The long time exponential relaxation is associated with complete randomization of pseudonematic domains. We examine the effect of local orientational correlation on spectral diffusion (structural evolution) experienced by a vibrational probe molecule within the pseudonematic domains of 4-cyano-4'-pentylbiphenyl (5CB) using two-dimensional infrared (2D IR) vibrational echo spectroscopy. The addition of low concentration 4-pentyl-4'-thiocyanobiphenyl (5SCB) as a long-lived vibrational probe to 5CB is shown to lower TNI of the sample slightly, but the fast power law dynamics and exponential decays observed by OHD-OKE spectroscopy are unchanged. We compare the complete orientational relaxation and spectral diffusion for samples of 5SCB in 5CB to 5SCB in 4-pentylbiphenyl (5B) at four temperatures above TNI. 5B has a molecular structure similar to 5CB but is not a nematogen. At all but the lowest temperature, the spectral diffusion in 5CB and 5B is described well as a triexponential decay with very similar time constants. The results demonstrate that the presence of local orientational order at temperatures well above TNI does not affect the spectral diffusion (structural evolution) within pseudonematic domains when the correlation lengths are short. However, when the temperature of the sample is held very close to TNI, the spectral diffusion in 5CB slows dramatically while that in 5B does not. It is only as the correlation length becomes very long that its presence impacts the spectral diffusion (structural fluctuations) sensed by the vibrational probes located in pseudonematic domains. The orientational relaxation is modeled with schematic mode coupling theory (MCT). Fitting with MCT provides density and orientational correlation functions. The density correlation decays are similar for 5B and 5CB, but the orientational correlation decays are much slower for 5CB. Additionally, the time dependence of the spectral diffusion in 5CB is strikingly similar to that of the density correlation function decay, while the orientational correlation function decay is far too slow to contribute to the spectral diffusion. Therefore, density fluctuations are likely the source of spectral diffusion at temperatures at least 5 K above TNI.
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