Role of complex formation in metal deposition - a theoretical study

金属沉积是电化学中的一个基本过程，具有重要的实用价值。直到最近，这类反应的动力学还没有在原子水平上被理解，因此一些同事谈到了金属沉积的谜团。申请人已经为水溶液中的小的单价金属离子解开了这个谜团，但多价离子仍然是一个谜。由于能量的原因，电子一次只能转移一个，但中间溶剂化离子的能量几乎总是如此之高，以至于第一次电子转移将非常不利。根据许多实验证据，我们推测，这些中间态的能量因金属络合物的形成而降低，通常是与阴离子形成的。我们希望通过结合密度泛函理论、分子动力学和我们自己的理论来研究这一机制，该理论必须扩展到包括络合物的形成。非水溶剂通常提供比水更广泛的金属沉积潜在范围，因此将成为我们研究的中心。从相对简单的一价锂离子开始，我们将转移到更复杂的反应，如铜沉积，特别是从以太溶液中沉积镁，这对镁电池来说是重要的。在整个项目中，我们将与一个国际知名的组织合作，他们对这些过程进行实验研究。我们相信，我们的项目将提供对一类电化学反应的基本了解，这类电化学反应目前是电池研究的重点。这两位申请者已经合作了十多年，组成了一支经验丰富的团队，专业知识互补。

Metal deposition is a fundamental process in electrochemistry and of great practical importance. Until very recently, the kinetics of this class of reactions was not understood at an atomic level, so that some colleagues spoke of the enigma of metal deposition. The applicants have solved this enigma for the case of small, univalent metal ions in aqueous solutions, but multivalent ions remain a puzzle. For energetic reasons electrons can only be transferred one at a time, but the energies of the intermediate solvated ions are almost always so high, that the first electron transfer would be highly unfavorable. In accord with much experimental evidence we surmise that the energies of these intermediate states are lowered by the formation of metal complexes, typically with anions. We want to investigate this mechanism by a combination of density functional theory, molecular dynamics, and our own theory, which must be extended to include complex formation. Non aqueous solvents often offer a wider potential range for metal deposition than water, and will therefore be at the center of our investigations.Starting from the relatively simple case of the monovalent lithium ion, we shall move on to more complex reactions like copper deposition, and in particular to magnesium deposition from etherial solutions, which is important for magnesium batteries. Throughout this project we shall cooperate with a group of international renown, which investigates these processes experimentally. We are confident that our project will provide a fundamental understanding of a class of electrochemical reactions which at present is the focus of battery research. The two applicants have been cooperating for more than a decade, and form an experienced team with complementing expertise.