Solvation at Aqueous Metal Electrodes

We present a study of the solvation properties of model aqueous electrode interfaces. The exposed electrodes we study strongly bind water and have closed packed crystalline surfaces, which template an ordered water adlayer adjacent to the interface. We find that these ordered water structures facilitate collective responses in the presence of solutes that are correlated over large lengthscales and across long timescales. Specifically, we show that the liquid water adjacent to the ordered adlayers forms a soft, liquid-vapor-like interface with concomitant manifestations of hydrophobicity. Temporal defects in the adlayer configurations create a dynamic heterogeneity in the degree to which different regions of the interface attract hydrophobic species. The structure and heterogeneous dynamics of the adlayer defects depend upon the geometry of the underlying ordered metal surface. For both 100 and 111 surfaces, the dynamical heterogeneity relaxes on times longer than nanoseconds. Along with analyzing time scales associated with these effects, we highlight implications for electrolysis and the particular catalytic efficiency of platinum.Comment: 9 pages, 8 figure

Microscopic dynamics of charge separation at the aqueous electrochemical interface

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na$^+$I$^-$, or classical ions, and the products of water autoionization, H$_3$O$^+$OH$^-$, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. Despite this, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free energy barrier to charge separation and a smaller flux over that barrier at the interface, results in a rate of dissociation that is 40x slower relative to the bulk. For water ions, a slightly higher free energy barrier is offset by a higher flux over the barrier from longer lived hydrogen bonding patters at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.Comment: 6 pages, 3 figures + S

The \u27Right\u27 to Break a Contract

It is common knowledge that the fully developed common law affords no means to compel the performance of a contract according to its terms. Does it follow from this that there is no legal obligation to perform a contract, or if obligation there be, that it is alternative: to perform or pay damages? A note in the XIV MICH. L. REV. 480 appears to give an affirmative answer to this question and at least one court (Frye v. Hubbell, 74 N. H. 358, at p. 374) has taken the same view. Probably the most forcible exposition of this position is given by Justice Holmes in his admirable address, THE PATH OF THE LAW (10 HARV. L. REV. at p. 462). The passage is sufficiently picturesque to deserve quotation: Nowhere is the confusion between legal and moral ideas more manifest than in the law of contract. Among other things, here again the so called primary rights and duties are invested with a mystic significance beyond what can be assigned and explained. The duty to keep a contract at common law means a prediction that you must pay damages if you do not keep it,-and nothing else. If you commit a tort, you are liable to pay a compensatory sum. If you commit a contract, you are liable to pay a compensatory sum unless the promised event comes to pass, and that is all the difference. But such a mode of looking at the matter stinks in the nostrils of those who think it advantageous to get as much ethics into the law as they can. It was good enough for Lord Coke, however, and here, as in many other cases, I am content to abide with him

Reconstruction of industrial piping installations from laser point clouds using profiling techniques

Includes abstract.Includes bibliographical references (leaves 143-152).As-built models of industrial piping installations are essential for planning applications in industry. Laser scanning has emerged as the preferred data acquisition method of as built information for creating these three dimensional (3D) models. The product of the scanning process is a cloud of points representing scanned surfaces. From this point cloud, 3D models of the surfaces are reconstructed. Most surfaces are of piping elements e.g. straight pipes, t-junctions, elbows, spheres. The automatic detection of these piping elements in point clouds has the greatest impact on the reconstructed model. Various algorithms have been proposed for detecting piping elements in point clouds. However, most algorithms detect cylinders (straight pipes) and planes which make up a small percentage of piping elements found in industrial installations. In addition, these algorithms do not allow for deformation detection in pipes. Therefore, the work in this research is aimed at the detection of piping elements (straight pipes, elbows, t-junctions and flange) in point clouds including deformation detection

Full Faith and Credit and Jurisdiction

The judgment of a sister state, when assailed by collateral attack, is often said to occupy a position intermediate between foreign and domestic judgments. Though the older American cases were inclined to examine into the merits of any foreign judgment, the present tendency is toward the adoption of the English view according to which a foreign judgment may be attacked collaterally only for want of jurisdiction or fraud. Dicey, Conflict of Laws (ed. 2) Ch. XVII; see note to Tremblay v. Aetna Life Insurance Co., 97 Me. 547, in 94 Am. St. Rep. 521, 538. But whereas any statement of jurisdictional facts in a foreign judgment is presumptive only, a domestic judgment is free from collateral attack on the ground of jurisdiction, except where lack of jurisdiction appears upon the face of the record. I BLACK, JUDGMENTS (ed. 2), § 274. The courts of New York have declined to accord this favoured position to domestic judgments and apparently make no distinction between domestic judgments and those of a sister state in this matter. Ferguson v. Crawford, 70 N. Y. 253, 26 Am. Rep. 589. In view of the so-called \u27full faith and credit clause\u27 of the constitution (Art. IV, §1), it is difficult to see why the judgment of a sister state should be open to any form of collateral attack to which it is not open in the state where the judgment is rendered. This would seem to follow from the familiar statement of Chief Justice Marshall in Hampton v. McConnel, 3 Wheat. 234 (affirming the doctrine of Mills v. Duryee, 7 Cranch 481), which in the opinion of Justice Holmes is still a correct exposition of the law. Fauntleroy v. Lum, 210 U. S. 230, 236-7

The \u27Right\u27 to Break a Contract

It is common knowledge that the fully developed common law affords no means to compel the performance of a contract according to its terms. Does it follow from this that there is no legal obligation to perform a contract, or if obligation there be, that it is alternative: to perform or pay damages? A note in the XIV MICH. L. REV. 480 appears to give an affirmative answer to this question and at least one court (Frye v. Hubbell, 74 N. H. 358, at p. 374) has taken the same view. Probably the most forcible exposition of this position is given by Justice Holmes in his admirable address, THE PATH OF THE LAW (10 HARV. L. REV. at p. 462). The passage is sufficiently picturesque to deserve quotation: Nowhere is the confusion between legal and moral ideas more manifest than in the law of contract. Among other things, here again the so called primary rights and duties are invested with a mystic significance beyond what can be assigned and explained. The duty to keep a contract at common law means a prediction that you must pay damages if you do not keep it,-and nothing else. If you commit a tort, you are liable to pay a compensatory sum. If you commit a contract, you are liable to pay a compensatory sum unless the promised event comes to pass, and that is all the difference. But such a mode of looking at the matter stinks in the nostrils of those who think it advantageous to get as much ethics into the law as they can. It was good enough for Lord Coke, however, and here, as in many other cases, I am content to abide with him