International Research Fellowship Program: Ab Initio Study of Aqueous Polyions

0903342 Bogatko该奖项是根据2009年美国复苏和再投资法案（公法111-5）资助的。国际研究奖学金计划使美国科学家和工程师能够在国外进行9到24个月的研究。 该计划的奖项提供了联合研究的机会，以及使用独特或互补的设施，专业知识和国外的实验条件。Bogatko与比利时布鲁塞尔自由大学的Paul Geerlings博士合作。新的工业和能源技术对环境的影响是当今公众讨论的主要话题。 最令人关切的是有毒物质可能从工业场所或封闭设施迁移到生物圈。 铝（III）离子是特别重要的，因为它存在于重要工业活动的副产品中，例如加工铝土矿以形成纯氧化铝和从深层矿床中回收烃。 不幸的是，它也是一种已知的神经毒素，破坏植物和动物的基本生物过程，并可能在阿尔茨海默病中发挥作用。的疾病。 与水相接触无疑将在有毒铝物种的迁移中发挥重要作用。 在溶液中，Al 3+以多种氧代羟基多离子形式存在，如[Al（H2O）6]3+、[Al 2（OH）2（H2O）8]4+、[Al 3（OH）4（H2O）9]5+、[Al 4（OH）6（H2O）11]6+、[Al 4 O（OH）5（H2O）10]5+和[Al O 4Al 12（OH）24（H2O）12]7+。 这些物种的化学反应性决定了是否会发生进一步的聚合、解离或吸附在矿物表面。 本研究针对这些问题。 这些物种的反应性指数，如亲核性，亲电性和化学硬度，使用高层次的量子化学方法在各种水性环境中，包括溶液pH值，反离子，温度和压力的影响进行评估。 由于这些系统的复杂性，实验方法的成功有限。 第一原理理论研究因此成为一个宝贵的工具，不仅补充实验数据，而且在预测新的属性。一个现实的模拟提出了一个重大的计算挑战，因为大量的原子需要模拟的溶剂化效应和一个有效的和高层次的分子动力学算法需要使用，包括温度和压力的影响。 这是使用概念密度泛函理论（CDFT）方法，其概念已开发和实施的Vrije大学布鲁塞尔（VUB）的Paul Geerlings教授，和高性能赝势平面波密度泛函理论（PSPW-DFT）算法开发的加州圣地亚哥大学（UCSD）的John Weare教授。这些方法的加入代表了量子计算化学领域的一个重要步骤，该领域的目标是产生高度准确的，定量的化学信息的系统，其大小和复杂性代表？最先进的技术？

0903342BogatkoThis award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).The International Research Fellowship Program enables U.S. scientists and engineers to conduct nine to twenty-four months of research abroad. The program's awards provide opportunities for joint research, and the use of unique or complementary facilities, expertise and experimental conditions abroad.This award will support a twenty-four-month research fellowship by Dr. Stuart A. Bogatko to work with Dr. Paul Geerlings at Free University of Brussels in Belgium.The environmental impact of new industrial and energy technologies is today a main subject of public discussion. Of prime concern is the possible migration of toxic material from industrial sites or containment facilities into the biosphere. The Aluminum(III) ion is of particular importance because it is found in the by-products of important industrial activities such as processing of bauxite to form pure alumina and the reclamation of hydrocarbons from deep deposits. Unfortunately it is also a known neurotoxin disrupting essential biological processes in plants and animals and may possibly play a role in Alzheimer?s disease. Contact with the aqueous phase would undoubtedly play a major role in the migration of toxic aluminum species. In solution Al3+ exists in a variety of oxohydroxo polyion species such as [Al(H2O)6]3+, [Al2(OH)2(H2O)8]4+, [Al3(OH)4(H2O)9]5+, [Al4(OH)6(H2O)11]6+, [Al4O(OH)5(H2O)10]5+ and [AlO4Al12(OH)24(H2O)12]7+. The chemical reactivity of these species determines whether further polymerization, dissociation or adsorption on mineral surfaces will occur. This study addresses these concerns. The reactivity indices, such as nucleophilicity, electrophilicity and chemical hardness, of these species are evaluated using high level quantum chemistry methods in a variety of aqueous environments including effects of solution pH, counter-ions, temperature and pressure. Experimental methods have seen limited success due to the complexity of these systems. First principles theoretical investigations have thus become an invaluable tool not only supplementing experimental data but also in prediction of new properties. A realistic simulation poses a significant computational challenge because a large number of atoms are required to model the solvation effects and an efficient and high level molecular dynamics algorithm needs to be used to include the effects of temperature and pressure. This is achieved using the Conceptual Density Functional Theory (CDFT) methods, whose concepts have been developed and implemented by Professor Paul Geerlings of Vrije Universiteit Brussels (VUB), and the high performance Pseudo-Potential Plane-Wave Density Functional Theory (PSPW-DFT) algorithms developed by Professor John Weare of the University of California San Diego (UCSD). The joining of these methods represents a major step in the field of Quantum Computational Chemistry towards producing highly accurate, quantitative chemical information of a system whose size and complexity represents the ?state of the art?.