Transitions between Inherent Structures in Water

The energy landscape approach has been useful to help understand the dynamic properties of supercooled liquids and the connection between these properties and thermodynamics. The analysis in numerical models of the inherent structure (IS) trajectories -- the set of local minima visited by the liquid -- offers the possibility of filtering out the vibrational component of the motion of the system on the potential energy surface and thereby resolving the slow structural component more efficiently. Here we report an analysis of an IS trajectory for a widely-studied water model, focusing on the changes in hydrogen bond connectivity that give rise to many IS separated by relatively small energy barriers. We find that while the system \emph{travels} through these IS, the structure of the bond network continuously modifies, exchanging linear bonds for bifurcated bonds and usually reversing the exchange to return to nearly the same initial configuration. For the 216 molecule system we investigate, the time scale of these transitions is as small as the simulation time scale ($\approx 1$ fs). Hence for water, the transitions between each of these IS is relatively small and eventual relaxation of the system occurs only by many of these transitions. We find that during IS changes, the molecules with the greatest displacements move in small ``clusters'' of 1-10 molecules with displacements of $\approx 0.02-0.2$ nm, not unlike simpler liquids. However, for water these clusters appear to be somewhat more branched than the linear ``string-like'' clusters formed in a supercooled Lennar d-Jones system found by Glotzer and her collaborators.Comment: accepted in PR

Time and length scales in supercooled liquids

We numerically obtain the first quantitative demonstration that development of spatial correlations of mobility as temperature is lowered is responsible for the ``decoupling'' of transport properties of supercooled liquids. This result further demonstrates the necessity of a spatial description of the glass formation and therefore seriously challenges a number of popular alternative theoretical descriptions.Comment: 4 pages, 4 figs; improved version: new refs and discussion

Synthesis and properties of ambient temperature molten salts based on the quaternary ammonium ion

The synthesis of 16 tetraalkyl ammonium bis(trifluoromethane sulfonyl) imide salts, (CnH2n+1)4 +N -N (SO2CF3)2 (n = 1, 2, 3, 4),&nbsp; (C2H5)2(i-C3H7)2 +N -N(SO2CF3)2, (C2H5)(CH3)(i-C3H7)2+N-N(SO2CF3)2, (n-C7H15)(C2H5)i-C3H7)2+N-N(SO2CF3)2 and (CnH2n+1)(CmH2m+1)3+N-N(SO2CF3)2 (n = 6,7,8; m = 1, 2, 4) are reported in this paper. Trends in properties of these salts are discussed. The symmetrical tetraalkyl ammonium salts with the bis(trifluoromethyl sulfonyl) imide anion exhibited a lower melting point than that of corresponding ammonium halides. The salts with low symmetry ammonium cations were found to be of generally lower melting point, and many were stable liquids at room temperature. Several of these did not crystallize during cooling below room temperature and exhibited glass transition temperatures in the region of &minus;60 &deg;C&sim;&minus;80 &deg;C. A comparison of properties between the ammonium imide salts and corresponding trifluoromethane sulfonates is also presented. <br /

The production of ultrafine ferrite during hot torsion testing of a 0.11 Wt Pct C steel

Ultrafine ferrite grain sizes were produced in a 0.11C-1.6Mn-0.2Si steel by torsion testing isothermally at 675 &deg;C after air cooling from 1250 &deg;C. The ferrite was observed to form intragranularly beyond a von Mises equivalent tensile strain of approximately 0.7 to 0.8 and the number fraction of intragranular ferrite grains continued to increase as the strain level increased. Ferrite nucleated to form parallel and closely spaced linear arrays or &ldquo;rafts&rdquo; of many discrete ultrafine ferrite grains. It is shown that ferrite nucleates during deformation on defects developed within the austenite parallel to the macroscopic shear direction (i.e., dynamic strain-induced transformation). A model austenitic Ni-30Fe alloy was used to study the substructure developed in the austenite under similar test conditions as that used to induce intragranular ferrite in the steel. It is shown that the most prevalent features developed during testing are microbands. It is proposed that high-energy jogged regions surrounding intersecting microbands provide potential sites for ferrite nucleation at lower strains, while at higher strains, the walls of the microbands may also act as nucleation sites.<br /