At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It ...was predicted from theory-and later confirmed by experiment-that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states-an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
While radiation scattering data provides insight inside the microstructure of liquids, the Debye relation relating the scattering intensity
(
) to the atom-atom structure factorsSab(k)shows that, ...ultimately, it is these individual structure correlation functions which contain the relevant information about the micro-structure. However, these quantities are not observables, except in few cases where one can invert the Debye relation to obtain the structure functions. In the majority of other cases, the need for model dependent computer simulations is unavoidable. The resulting calculations reveal that the scattering pre-peak is the result of cancellations between positive pre-peaks and negative anti-peaks contributions from the atom-atom structure factors. What of systems where this cancellation is such that it entirely suppresses the scattering pre-peak? One would be tempted to falsely conclude that there is no underlying micro-heterogeneity. Hence, the structure functions appear as hidden variables, and it is important to understand the relation between their features and the micro-structure of the system. Through the computer simulation study of various mono-ols, ranging from methanol to 1-nonanol, as well as the branched octanols, we show how the features of the atom-atom pair correlation functiongab(r)affect that of the structure factorsSab(k), and reveal that the micro-structure is ultimately the result of the charge ordering between different atoms in the system.
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 (CnmimNTf2), 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 beta-relaxation mode and the intermediate- and high-frequency components to librational modes.
A multiscale coarse-graining model for ionic liquids has been extended to investigate the unique aggregation of cations in ionic liquids through computer simulation. It has been found that, with ...sufficiently long side chains, the tail groups of cations aggregate to form spatially heterogeneous domains, while headgroups of the cations and the anions distribute as uniformly as possible. This is understood as the result of competition between the charged electrostatic interactions between headgroups and anions and the collective short-range interactions between the neutral tail groups. This aggregation can help to explain a number of experimentally observed physical phenomena in ionic liquids.
X-ray scattering experiments and molecular dynamics simulations have been performed to investigate the structure of four room temperature ionic liquids (ILs) comprising the ...bis(trifluoromethylsulfonyl)amide (NTf2 –) anion paired with the triethyloctylammonium (N2228 +) and triethyloctylphosphonium (P2228 +) cations and their isoelectronic diether analogs, the (2-ethoxyethoxy)ethyltriethylammonium (N222(2O2O2) +) and (2-ethoxyethoxy)ethyltriethylphosphonium (P222(2O2O2) +) cations. Agreement between simulations and experiments is good and permits a clear interpretation of the important topological differences between these systems. The first sharp diffraction peak (or prepeak) in the structure function S(q) that is present in the case of the liquids containing the alkyl-substituted cations is absent in the case of the diether substituted analogs. Using different theoretical partitioning schemes for the X-ray structure function, we show that the prepeak present in the alkyl-substituted ILs arises from polarity alternations between charged groups and nonpolar alkyl tails. In the case of the diether substituted ILs, we find considerable curling of tails. Anions can be found with high probability in two different environments: close to the cationic nitrogen (phosphorus) and also close to the two ether groups. For the two diether systems, anions are found in locations from which they are excluded in the alkyl-substituted systems. This removes the longer range (polar/nonpolar) pattern of alternation that gives rise to the prepeak in alkyl-substituted systems.
Ionic liquids with intermediate nonpolar cationic side-chain lengths are known to have nanoscale spatial heterogeneities with nonpolar tail domains separated by a continuous polar network. In this ...work, we use coarse-grained molecular dynamics simulations to show that, when the nonpolar cationic side chain is sufficiently long, due to the stronger van der Waals interactions between the side chains, the structure of ionic liquids goes through a transition from spatially heterogeneous to liquid crystalline-like. For XMIm+/NO3 – ionic liquids, change occurs when the number of carbon groups on the cationic side chain varies from 14 to 16. In the liquid crystal-like phase, the cationic side chains tend to be parallel to each other, while the cationic head groups and anions, although being mostly layered perpendicularly to the direction along the side chains, still form a continuous polar network.
High-energy x-rays from a synchrotron radiation source allow us to obtain high-quality diffraction data for disordered materials from ambient to extreme conditions, which is necessary for revealing ...the detailed structures of glass, liquid and amorphous materials. We introduced high-energy x-ray diffraction beamlines and a dedicated diffractometer for glass, liquid and amorphous materials at SPring-8 and report the recent developments of ancillary equipment. Furthermore, the structures of liquid and amorphous materials determined from the high-energy x-ray diffraction data obtained at SPring-8 are discussed.
X-ray diffraction data on liquids and disordered solids often provide useful complementary structural information to neutron diffraction data. Interpretation of the x-ray diffraction pattern, which ...is produced by scattering from the atomic electrons rather than from the atomic nuclei as in the case of neutron diffraction, is, however, complicated by the Q-dependent electronic form factors, which cause the x-ray diffraction signal to decline rapidly with increasing Q, where Q is the wave vector change in the diffraction experiment. The problem is particularly important in cases such as water where there is a significant molecular polarization caused by charge transfer within the molecule. This means that the electron form factors applicable to the molecule in the condensed environment often deviate from their free atom values. The technique of empirical potential structure refinement (EPSR) is used here to focus on the problem of forming a single atomistic structural model which is simultaneously consistent with both x-ray and neutron diffraction data. The case of liquid water is treated explicitly. It is found that x-ray data for water do indeed provide a powerful constraint on possible structural models, but that the Q-range of the different x-ray data sets (maximum Q ranges from 10.8 to ∼17.0 Å(-1) for different x-ray experiments), combined with variations between different data sets, means that it is not possible to rigorously define the precise position and height of the first peak in the OO radial distribution function. Equally, it is found that two different neutron datasets on water, although measured to a maximum Q of at least 30 Å(-1), give rise to further small uncertainties in the position of the hydrogen bond peaks. One general conclusion from the combined use of neutron and x-ray data is that many of the classical water potentials may have a core which is too repulsive at short distances. This produces too sharp a peak in r-space at too short a distance. A softer core potential is proposed here.
We have studied the electronic structure of liquid water using x-ray absorption spectroscopy at the oxygen K edge. Since the x-ray absorption process takes less than a femtosecond, it allows probing ...of the molecular orbital structure of frozen, local geometries of water molecules at a timescale that has not previously been accessible. Our results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms, resulting in a pronounced pre-edge feature below the main absorption edge in the spectrum. Theoretical calculations of these spectra suggest that this feature originates from specific configurations of water, for which the H-bond is broken on the H-donating site of the water molecule. This study provides a fingerprint for identifying broken donating H-bonds in the liquid and shows that an unsaturated H-bonding environment exists for a dominating fraction of the water molecules.
From the extension of the concepts used in our three previous works (B. Grosdidier 2018, 2019, 2021), we investigate the structure and calculate the order parameters in the quaternary alloy. We show ...that the order may be described by two conceptualizations as for the ternary alloy. All structural quantities and the relationships between them are calculated. In the frame of our approach, we propose a new and more concise formula of the order parameters. We check the consistency of our approach on several “toys models” having specific behaviour of their atomic species. All order parameters are calculated in both conceptualizations. Some of them are plotted on tetrahedral quaternary phase diagrams. We retrieve our results by studying the atom exchanges in several kinds of iso-stoichiometric quaternary alloys. We describe several properties specific to the quaternary alloy that do not exist in binary or in ternary alloys.
•Existence of two conceptualizations of the order in the quaternary alloy.•Calculation of the structure factors in both conceptualizations.•Elaboration of a new and more concise formula of the order parameters.•Calculation of the order in six “toy models” and in four iso-stoichiometric quaternary alloys.•Highlighting of order properties specific to the quaternary system.
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