Monohydroxy alcohols have been in the focus of scientific research for a long time and their Debye (-like) process was studied predominantly using dielectric spectroscopy. However, a number of other techniques are useful to unravel the dynamics of these supramolecular liquids. For a recent review on neat monohydroxy alcohols, see R. Böhmer, C. Gainaru, R. Richert, Phys. Rep. (accepted). On this background the present article deals mostly with mixtures involving monohydroxy alcohols using various experimental methods. Examples given include dielectric spectroscopy on a mixture which shows a small Debye process well separated from the structural relaxation. For another mixture it is demonstrated that the time scales of the dielectric and the rheological signatures of the Debye process coincide. Isotope labeling is exploited to map out the rotational dynamics of both components in binary mixtures of 1-butanol (BuOH) and 1-bromobutane (BuBr) using spin–lattice relaxation nuclear magnetic resonance (NMR) spectroscopy. While the hydroxyl motion in BuOH becomes faster upon admixture of BuBr, the alkyl bromide dynamics is virtually independent of composition. Two-time and four-time stimulated-echo NMR experiments show that the dynamic exchange in a BuOH–BuBr mixture is similar to that of supercooled liquids devoid of a Debye process and hence it does not provide a rationale to understand the symmetric broadening of the structural dielectric loss peak in this and related mixtures. Finally, a wavelength dependent derivative analysis of near-infrared spectra recorded for pure and mixed monohydroxy alcohols over wide temperature ranges shows that the rearrangement of the hydrogen network differs below and above about 250K.

Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

The relatively small dielectric Debye-like process of the monohydroxy alcohol 4-methyl-3-heptanol (4M3H) was found to depend slightly on the intramolecular conformation. Proton and deuteron nuclear magnetic resonance demonstrate that the hydroxyl dynamics and the overall molecular dynamics take place on similar time scales in contrast to the situation for the structural isomer 2-ethyl-1-hexanol (2E1H) [S. Schildmann et al., J. Chem. Phys. 135, 174511 (2011)]. This indicates a very weak decoupling of Debye-like and structural relaxation which was further probed using volume expansivity experiments. Shear viscosity as well as diffusometry measurements were performed and the data were analyzed in terms of the Debye-Stokes-Einstein equations. In mixtures of 4M3H with 2E1H the Debye-like process becomes much stronger and for 2E1H mole fraction of more than 25% the behavior of this alcohol is rapidly approached. This finding is interpreted to indicate that the ring-like supramolecular structures in 4M3H become energetically unfavorable when adding 2E1H, an alcohol that tends to form chain-like molecular aggregates. The concentration dependence of the Kirkwood factor in these mixtures displays a high degree of similarity with experimental results on monohydroxy alcohols in which the pressure or the location of the OH group within the molecular structure is varied.

Water doped with 10−2 mol of KOH was cooled to temperatures at which most of the solution freezes to form hexagonal ice. Using proton and deuteron spin–lattice relaxometry as well as static field gradient diffusometry, it was found that a liquid-like phase coexists with the crystal down to below 200 K. The ionic dopants are expelled from the crystalline phase and form a KOH-enriched aqueous solution probably in the form of inclusions within the ice crystal. Its self-diffusion coefficient is only slightly smaller than that of nominally pure water. Motional correlation times were determined on the basis of spin–lattice relaxation times and compared with previous electrical conductivity and calorimetry results.

Using deuteron nuclear magnetic resonance and dielectric spectroscopy KOH doped tetrahydrofuran clathrate hydrates and KOH doped hexagonal ice are studied at temperatures above 60 and 72 K, respectively. Below these temperatures proton order is established on the lattice formed by the water molecules. In the clathrate hydrate a new type of small-angle motion is discovered using deuteron spin-spin relaxation, line-shape analysis, and stimulated-echo experiments. Based on the latter results a model is developed for the local proton motion that could successfully be tested using random-walk simulations. It is argued that the newly identified small-angle motion, obviously absent in undoped samples, is an important feature of the mechanism which accompanies the establishment of proton order not only in doped clathrate hydrates but also in doped hexagonal ice. Specific motions of OH(-) defects are demonstrated to explain the experimentally observed behavior. The relative importance of localized versus delocalized OH(-) defect motions is discussed.

The spectral densities related to various relaxation processes of the glass former 2-ethyl-1-hexanol (2E1H), a monohydroxy alcohol, are probed using several nuclear magnetic resonance (NMR) experiments as well as via dielectric noise spectroscopy (DNS). On the basis of the spectral density relating to voltage fluctuations, i.e., without the application of external electrical fields, DNS enables the detection of the structural relaxation and of the prominent, about two decades slower Debye process. The NMR-detected spectral density, sensitive to the orientational fluctuations of the hydroxyl deuteron, also reveals dynamics slower than the structural relaxation, but not as slow as the Debye process. Rotational and translational correlation functions of 2E1H are probed using stimulated-echo NMR techniques which could only resolve the structural dynamics or faster processes. The experimental results are discussed with reference to models that were suggested to describe the dynamics in supercooled alcohols.

Dielectric loss spectra covering 13 decades in frequency were collected for 2-ethyl-1-hexanol, a monohydroxy alcohol that exhibits a prominent Debye-like relaxation, typical for several classes of hydrogen-bonded liquids. The thermal variation of the dielectric absorption amplitude agrees well with that of the hydrogen-bond equilibrium population, experimentally mapped out using near infrared (NIR) and nuclear magnetic resonance (NMR) measurements. Despite this agreement, temperature-jump NIR spectroscopy reveals that the hydrogen-bond switching rate does not define the frequency position of the prominent absorption peak. This contrasts with widespread notions and models based thereon, but is consistent with a recent approach.

The host as well as the guest dynamics in ion doped clathrate hydrates were studied via several deuteron nuclear magnetic resonance techniques and using broadband dielectric spectroscopy in conjunction with the application of large electrical fields. At a given temperature evidence for up to three relaxation processes was found for samples with mole fractions larger than 10(-4) KOH. The two slower processes, unraveled via an electrical cleaning procedure, are similar to those detected on undoped samples in which they proceed on slightly longer time scales. The fastest process exhibits a weak temperature dependence except close to the transition into the low-temperature phase. Here, an incomplete proton order is established on the hydrate lattice and a residual orientational motion of the guest molecules could be detected at low temperatures. These results demonstrate the large degree of coupling between host and guest motions.

Monohydroxy alcohols show a structural relaxation and at longer time scales a Debye-type dielectric peak. From spin-lattice relaxation experiments using different nuclear probes, an intermediate, slower-than-structural dynamics is identified for n-butanol. Based on these findings and on translational diffusion measurements, a model of self-restructuring, transient chains is proposed. The model is demonstrated to explain consistently the so-far puzzling observations made for this class of hydrogen-bonded glass forming liquids.

The guest dynamics in tetrahydrofuran (THF) clathrate hydrate (THF center dot 17H(2)O) was studied using several deuteron nuclear magnetic resonance (NMR) techniques. At low temperatures the magnetization recovery proceeds in two steps. The weight of the faster contribution decreases with decreasing temperatures. This behavior is the signature of a dynamical effect. The two contributions cannot be ascribed separately to the metadeuteron and to the paradeuteron of the THF molecule. The thermal evolution of the NMR spectra was described semiquantitatively using a distorted octahedral reorientational jump model. Pseudorotation has no significant impact on the spectral width. The motional correlation times, measured using two-time stimulated-echo and spin-relaxation techniques, cover a dynamic range of nine decades. Four-time stimulated-echo measurements reveal a statically heterogeneous rotational motion of the guest molecules in the 16-faced polyhedral cages of the structure II lattice.

Deuteron nuclear magnetic resonance (NMR) and dielectric spectroscopy are utilized to investigate the dynamics of the water molecules in the semiclathrate (tetra-n-butyl ammonium bromide) 26 H(2)O. Stimulated-echo spectroscopy reveals a nonexponential correlation function predominantly due to rotational motion with jump angles that are broadly distributed around the tetrahedral angle. The reorientational correlation times from this technique agree excellently with those from dielectric measurements, both resulting in an activation energy of (43+/-1) kJ/mol. Large, spatially varying electrical dipolar fields, set up by the Br(-) and the N(+) ions located on the hydrate lattice, are held responsible for the pronounced stretching of the correlation functions. Solid-echo spectra were acquired over a broad temperature range. They exhibit an apparent two-phase character discussed in terms of various scenarios. Two-dimensional NMR spectra and four-time stimulated echoes were recorded, but an exchange of slow and fast subensembles could not be detected. Spin-lattice relaxation does not directly reflect the local reorientational motion and its nonexponentiality is interpreted with reference to the translational dynamics of the water molecules.