Model Core Potentials: Development and Applications

化学反应有赖于价电子之间的相互作用，如元素周期表中的列所示，其中化学相关的原子族共享相同的价电子配置。在理论/计算化学中，这一性质导致了赝势方法的产生，这种方法消除了化学惰性的核心电子，减少了计算时间，并允许研究含有重原子的非常大的分子。*在我们的实验室中，我们发展了赝势方法的高级版本，模型芯势(MCP)方法。MCP方法允许准确预测小分子、中型有机金属络合物和具有生化重要性的体系中的性质和相互作用。该方法通过描述新分子在实验中被发现之前的性质，展示了它的预测能力。*我们的长期目标是通过以下方式推进MCP方法：*·为研究激发态和核磁共振参数准备MCP参数*·开发MCP代码，该代码将通过使用图形处理单元来加速*·使用MCP方法设计新的分子系统。*几个应用领域的短期目标将包括：*·分子和分子离子的激发电子态：我们将探索含有重原子的大分子的低激发电子态。我们将设计新的硫取代冠醚，当它与荧光团连接时，将诱导依赖于重金属离子的身份的荧光，从而有助于离子的检测。*·稀有气体原子化学：我们将探索氡的化学，以确定可能是实验合成和检测的良好候选分子。我们将获得有关结构、振动谐和非谐光谱以及电子光谱的数据。*·重金属离子与有机分子的相互作用。我们将分析环境友好的糖脂生物表面活性剂之间的反应能量学，这些表面活性剂能够提取有毒的重金属离子。我们将确定金属离子对溶剂化分子的结构和光谱的影响。*·新型抗有丝分裂抗癌药物的设计：更好地了解微管和配体之间的相互作用在改进药物的设计中至关重要。这些分子系统非常大。幸运的是，并不是这些系统的所有部分都是平等的：重要的化学作用只发生在其中的一小部分，而其余的仅仅形成了一个分子框架。在相互作用的分析中，我们将使用新的MCP和碎片分子轨道方法进行分子动力学模拟。*我们目标的实现将使HQP有机会创建新的理论模型并将其应用于实际问题。*新的MCP参数和代码将在开源程序GamesS中提供。

Chemical reactions depend on the interactions between valence electrons, as shown in the columns of the Periodic Table of the elements, where families of chemically related atoms share identical valence electron configurations. In theoretical/computational chemistry, this property gave rise to pseudopotential methods that eliminate the chemically-inert core electrons, reduce computing time, and allow for the studies of very large molecules which contain heavy atoms.***In our laboratory we developed an advanced version of the pseudopotential method, the model core potential (MCP) method. The MCP method allows for accurate predictions of properties and interactions in small molecules, medium-size organometallic complexes, and systems of biochemical importance. The method has demonstrated its predictive power by describing properties of new molecules before they were discovered experimentally. ***Our long-term goal is to advance the MCP methodology by:***• preparing MCP parameters for the studies of excited states and NMR parameters***• developing MCP code that will be speeded up by using Graphics Processing Units***• designing novel molecular systems using the MCP method. ***Short-term objectives in several areas of applications will include:***• Excited electronic states of molecules and molecular ions: We will explore the low-lying excited electronic states of large molecules containing heavy atoms. We will design novel sulfur-substituted crown ethers which, when tethered to a fluorophore, will induce fluorescence that depends on the identity of the heavy metal ion thus aiding in the detection of the ion. ***• Chemistry of rare gas atoms: we will explore the chemistry of radon to identify molecules that might be good candidates for experimental synthesis and detection. We will obtain data about structure, vibrational harmonic and anharmonic spectra, and electronic spectra.***• Interactions between heavy metal ions and organic molecules. We will analyze energetics of reactions between the environmentally-friendly glycolipid biosurfactants that are capable of extracting toxic heavy metal ions. We will determine the effects of metal ions on the structure and spectra of solvated molecules.***• Design of new antimitotic anti-cancer drugs: A better understanding of the interactions between microtubules and ligands is critical in the design of improved drugs. These molecular systems are very large. Fortunately, not all parts of these systems are equal: important chemistry takes place only in a small part of them while the rest merely forms a molecular framework. In the analysis of interactions we will use the new MCPs together with fragment molecular orbital method in molecular dynamics simulations.***Realization of our goals will give the HQPs opportunities to create new theoretical models and apply them to practical problems.***The new MCP parameters and code will be available in the open-source program GAMESS.