Nuclear quantum effects in water exchange around lithium and fluoride ions

We employ classical and ring polymer molecular dynamics simulations to study the effect of nuclear quantum fluctuations on the structure and the water exchange dynamics of aqueous solutions of lithium and fluoride ions. While we obtain reasonably good agreement with experimental data for solutions of lithium by augmenting the Coulombic interactions between the ion and the water molecules with a standard Lennard-Jones ion-oxygen potential, the same is not true for solutions of fluoride, for which we find that a potential with a softer repulsive wall gives much better agreement. A small degree of destabilization of the first hydration shell is found in quantum simulations of both ions when compared with classical simulations, with the shell becoming less sharply defined and the mean residence time of the water molecules in the shell decreasing. In line with these modest differences, we find that the mechanisms of the exchange processes are unaffected by quantization, so a classical description of these reactions gives qualitatively correct and quantitatively reasonable results. We also find that the quantum effects in solutions of lithium are larger than in solutions of fluoride. This is partly due to the stronger interaction of lithium with water molecules, partly due to the lighter mass of lithium, and partly due to competing quantum effects in the hydration of fluoride, which are absent in the hydration of lithium.Comment: 12 pages, 8 figure

Mean-Field Theory of Water-Water Correlations in Electrolyte Solutions

Long-range ion induced water-water correlations were recently observed in femtosecond elastic second harmonic scattering experiments of electrolyte solutions. To further the qualitative understanding of these correlations, we derive an analytical expression that quantifies ion induced dipole-dipole correlations in a non-interacting gas of dipoles. This model is a logical extension of Debye-H\"uckel theory that can be used to qualitatively understand how the combined electric field of the ions induces correlations in the orientational distributions of the water molecules in an aqueous solution. The model agrees with results from molecular dynamics simulations and provides an important starting point for further theoretical work

Who\u27s in Charge of U.S. Indian Policy?: Congress and the Supreme Court at Loggerheads over American Indian Religious Freedom

The federal government\u27s three branches—executive, legislative, judicial, and that unwieldy mass known simply as the bureaucracy have, during the last half-decade—1987-1991—produced a dizzying crop of laws, policies, proclamations, regulations, and court decisions which have served simultaneously to 1) reaffirm tribal sovereignty; 2) permit and encourage greater state interference within Indian Country; 3) enhance federal legislative authority over tribes; and 4) deny constitutional free-exercise protections both to individual Indians and to tribes. On the legislative side, Congress has established the experimental Tribal Self-Governance Demonstration Project which is a major step towards restoring the tribal right of self-determination, and is discussing the potentiality of reestablishing a more constitutionally-grounded policy with tribes— New Federalism. This policy would resemble the bilateral agreement period between tribes and the U.S. which lasted from 1875 to 1914

Transformations in Supreme Court Thought: The Irresistible Force (Federal Indian Law & Policy) Meets the Movable Object (American Indian Tribal Status)

This article is a content analysis examination of 107 federal court cases involving American Indian tribal sovereignty and federal plenary power rendered between 1870 and 1921. Our focus, however, is the U.S. Supreme Court\u27s Indian Law jurisprudence; thus ninety of the cases analyzed were Supreme Court opinions. The cases seemingly entail two separate braces of opinions. One brace included decisions which affirmed tribal sovereignty. The other brace entailed cases which negatively affected tribal sovereignty. These negative decisions generally relied on doctrines such as plenary power, the political question doctrine, or the so- called “guardian-ward” relationship. We argue that the Supreme Court, as a partner in the ruling national alliance, generally deferred to the legislative branches during this critical historical era, Indian treaties and extra-constitutional rights notwithstanding. In seeking to explain the two separate, though not unrelated sets of opinions, we focus on the Court\u27s role in formulating public policy towards American Indian tribes in four major issue areas: congressional power, criminal law, allotment and membership, and natural resources. And we attempt to explain how and why the Court\u27s perception of these issues were transformed over time and how these changes affected tribal sovereign rights. Finally, we develop a synthetic, abstract model of judicial decision-making which provides some explanatory power regarding why the Court decides Indian related issues the way it does

Judicial Terror Confronts Indian Nations

As the Bush Administration broadens its constitutionally problematic assault on real and alleged terrorists, both home and abroad, endangering the very rights and liberties it accused Osama bin Laden of savagely attacking, the judicial branch of the government, occupied by a majority of conservative justices, is doing its part to shatter the sovereign rights and economic liberties of indigenous nations

Quit-Claiming the Doctrine of Discovery: A Treaty-Based Reappraisal

The discovery doctrine is one of the baseline legal concepts that has worked to seriously disadvantage the land rights of indigenous nations in the United States because it asserts, as one of its definitions, that the discovering European nations and their successor states, gained legal title to Indian lands in North America. The author argues, using comparative colonial and early American treaty, legislative, and other historical data, that this definition is a legal fiction. In historical reality, discovery was merely an exclusive and preemptive right that vested in the discovering state the right of first purchase

Will Tribes Ever Be Able to Trust Their Federal Trustee?

It is widely reported that the federal government has a trust relationship with the Indian peoples of this land, one of the many distinctive features of the indigenous/federal relationship. Despite the importance of this concept, legal and political commentators and, surprisingly, federal policy makers have radically conflicting definitions of what the trust relationship actually means

Tribes Paying Outsiders to Audit Their Membership

There is no greater responsibility for a tribal leader than to be a steward of their nation’s citizens/members. Yet in the area of constitutional reform and development, tribal membership, and enrollment policies and practices, many tribal governments have entrusted these most intimate of governmental responsibilities to outside organizations like CSN, Inc. (Constructing Stronger Nations)-DCIAmerica, the Harvard Project for American Indian Economic Development/Native Nations Institute, Automated Election Services, the Falmouth Institute, J. Dalton Institute, and others. In the case of membership, some of these for-profit organizations conduct, what I would suggest, are privacy invading enrollment audits

The Indigenous Vote: Protecting or Endangering Sovereignty?

Much ado has been made about the 2002 mid-term congressional and gubernatorial elections. Democrats are bemoaning the Republican\u27s treble triumph—congressional control, an invigorated Bush administration, and conservative rule on the supreme court. Republicans are exulting in their perceived conservative mandate—to address the War on Terror, privatize Social Security, and roll back environmental regulations that are deemed overly restrictive of private and public property development. And the inconsistent American voter, depending on race, socio-economic status, and issue salience, seems either unenthusiastic, ambivalent, or wildly animated about politics

Dismembered: Native Disenrollment and the Battle for Human Rights

While the number of federally recognized Native nations in the United States are increasing, the population figures for existing tribal nations are declining. This depopulation is not being perpetrated by the federal government, but by Native governments that are banishing, denying, or disenrolling Native citizens at an unprecedented rate. Since the 1990s, tribal belonging has become more of a privilege than a sacred right. Political and legal dismemberment has become a national phenomenon with nearly eighty Native nations, in at least twenty states, terminating the rights of indigenous citizens.The first comprehensive examination of the origins and significance of tribal disenrollment, Dismembered examines this disturbing trend, which often leaves the disenrolled tribal members with no recourse or appeal. At the center of the issue is how Native nations are defined today and who has the fundamental rights to belong. By looking at hundreds of tribal constitutions and talking with both disenrolled members and tribal officials, the authors demonstrate the damage this practice is having across Indian Country and ways to address the problem.https://scholarship.richmond.edu/bookshelf/1328/thumbnail.jp