175 research outputs found
Structural relaxation in the hydrogen-bonding liquids N-methylacetamide and water studied by optical Kerr-effect spectroscopy
Structural relaxation in the peptide model N-methylacetamide (NMA) is studied
experimentally by ultrafast optical Kerr-effect spectroscopy over the
normal-liquid temperature range and compared to the relaxation measured in
water at room temperature. It is seen that in both hydrogen-bonding liquids,
beta relaxation is present and in each case it is found that this can be
described by the Cole-Cole function. For NMA in this temperature range, the
alpha and beta relaxations are each found to have an Arrhenius temperature
dependence with indistinguishable activation energies. It is known that the
variations on the Debye function, including the Cole-Cole function, are
unphysical, and we introduce two general modifications: one allows for the
initial rise of the function, determined by the librational frequencies, and
the second allows the function to be terminated in the alpha relaxation
Phonon-like hydrogen-bond modes in protic ionic liquids
Gigahertz- to terahertz-frequency infrared and Raman spectra contain a wealth of information concerning the structure, intermolecular forces, and dynamics of ionic liquids. However, these spectra generally have a large number of contributions ranging from slow diffusional modes to underdamped librations and intramolecular vibrational modes. This makes it difficult to isolate effects such as the role of Coulombic and hydrogen-bonding interactions. We have applied far-infrared and ultrafast optical Kerr effect spectroscopies on carefully selected ions with a greater or lesser degree of symmetry in order to isolate spectral signals of interest. This has allowed us to demonstrate the presence of longitudinal and transverse optical phonon modes and a great similarity of alkylammonium-based protic ionic liquids to liquid water. The data show that such phonon modes will be present in all ionic liquids, requiring a reinterpretation of their spectra
The dynamic crossover in water does not require bulk water
Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquidâliquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that âbulkâ water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional StokesâEinstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to âworm-holeâ structure
Structure and dynamics in protic ionic liquids: a combined optical Kerr-effect and dielectric relaxation spectroscopy study
The structure and dynamics of ionic liquids (ILs) are unusual due to the strong interactions between the ions and counter ions. These microscopic properties determine the bulk transport properties critical to applications of ILs such as advanced fuel cells. The terahertz dynamics and slower relaxations of simple alkylammonium nitrate protic ionic liquids (PILs) are here studied using femtosecond optical Kerr-effect spectroscopy, dielectric relaxation spectroscopy, and terahertz time-domain spectroscopy. The observed dynamics give insight into more general liquid behaviour while comparison with glass-forming liquids reveals an underlying power-law decay and relaxation rates suggest supramolecular structure and nanoscale segregation
Glasslike Behavior in Aqueous Electrolyte Solutions
When salts are added to water, the viscosity generally increases suggesting
the ions increase the strength of the water's hydrogen-bond network. However,
infrared pump-probe measurements on electrolyte solutions have found that ions
have no influence on the rotational dynamics of water molecules implying no
enhance-ment or breakdown of the hydrogen-bond network. Here we report optical
Kerr-effect and dielectric relaxa-tion spectroscopic measurements, which have
enabled us to separate the effects of rotational and transitional motions of
the water molecules. These data show that electrolyte solutions behave like a
supercooled liquid approaching a glass transition in which rotational and
translational molecular motions are decoupled. It is now possible to understand
previously conflicting viscosity data, nuclear magnetic resonance relaxation,
and ultrafast infrared spectroscopy in a single unified picture
Detailed quantification of glacier elevation and mass changes in South Georgia
Most glaciers in South America and on the Antarctic Peninsula are retreating and thinning. They are considered strong contributors to global sea level rise. However, there is a lack of glacier mass balance studies in other areas of the Southern Hemisphere, such as the surrounding Antarctic Islands. Here, we present a detailed quantification of the 21st century glacier elevation and mass changes for the entire South Georgia Island using bi-static synthetic aperture radar interferometry between 2000 and 2013. The results suggest a significant mass loss since the beginning of the present century. We calculate an average glacier mass balance of -1.04 0.09 m w.e.a(-1) and a mass loss rate of 2.28 0.19 Gt a(-1) (2000-2013), contributing 0.006 0.001 mm a(-1) to sea-level rise. Additionally, we calculate a subaqueous mass loss of 0.77 0.04 Gt a(-1) (2003-2016), with an area change at the marine and lake-terminating glacier fronts of -6.58 0.33 km(2) a(-1), corresponding to similar to 4% of the total glacier area. Overall, we observe negative mass balance rates in South Georgia, with the highest thinning and retreat rates at the large outlet glaciers located at the north-east coast. Although the spaceborne remote sensing dataset analysed in this research is a key contribution to better understanding of the glacier changes in South Georgia, more detailed field measurements, glacier dynamics studies or further long-term analysis with high-resolution regional climate models are required to precisely identify the forcing factors
The beginning of time? Evidence for catastrophic drought in Baringo in the early nineteenth century
New developments in the collection of palaeo-data over the past two decades have transformed our understanding of climate and environmental history in eastern Africa. This article utilises instrumental and proxy evidence of historical lake-level fluctuations from Baringo and Bogoria, along with other Rift Valley lakes, to document the timing and magnitude of hydroclimate variability at decadal to century time scales since 1750. These data allow us to construct a record of past climate variation not only for the Baringo basin proper, but also across a sizable portion of central and northern Kenya. This record is then set alongside historical evidence, from oral histories gathered amongst the peoples of northern Kenya and the Rift Valley and from contemporary observations recorded by travellers through the region, to offer a reinterpretation of human activity and its relationship to environmental history in the nineteenth century. The results reveal strong evidence of a catastrophic drought in the early nineteenth century, the effects of which radically alters our historical understanding of the character of settlement, mobility and identity within the BaringoâBogoria basin
Comments on black holes I: The possibility of complementarity
We comment on a recent paper of Almheiri, Marolf, Polchinski and Sully who
argue against black hole complementarity based on the claim that an infalling
observer 'burns' as he approaches the horizon. We show that in fact
measurements made by an infalling observer outside the horizon are
statistically identical for the cases of vacuum at the horizon and radiation
emerging from a stretched horizon. This forces us to follow the dynamics all
the way to the horizon, where we need to know the details of Planck scale
physics. We note that in string theory the fuzzball structure of microstates
does not give any place to 'continue through' this Planck regime. AMPS argue
that interactions near the horizon preclude traditional complementarity. But
the conjecture of 'fuzzball complementarity' works in the opposite way: the
infalling quantum is absorbed by the fuzzball surface, and it is the resulting
dynamics that is conjectured to admit a complementary description.Comment: 34 pages, 6 figures, v3: clarifications & references adde
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