Model Core Potentials: Development and Applications

化学反应依赖于价电子之间的相互作用，如元素周期表列所示，化学相关的原子族共享相同的价电子构型。在理论/计算化学中，这种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，我们开发了伪势方法的高级版本，即模型核心势（MCP）方法。MCP方法可以准确预测小分子、中等大小的有机金属配合物和重要的生化系统的性质和相互作用。该方法通过描述新分子在实验中被发现之前的性质，证明了它的预测能力。***我们的长期目标是通过：*** **准备MCP参数用于激发态和核磁共振参数的研究*** **开发MCP代码，将通过使用图形处理单元加速*** **使用MCP方法设计新的分子系统。***在几个应用领域的短期目标将包括：*** *•分子和分子离子的激发态：我们将探索含有重原子的大分子的低洼激发态。我们将设计一种新的硫取代冠醚，当它与荧光基团相连时，将根据重金属离子的身份诱导荧光，从而有助于离子的检测。***•稀有气体原子的化学：我们将探索氡的化学性质，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、振动谐振谱和非谐振谱以及电子谱的数据。***•重金属离子与有机分子的相互作用。我们将分析能够提取有毒重金属离子的环境友好型糖脂生物表面活性剂之间反应的能量学。我们将确定金属离子对溶剂化分子的结构和光谱的影响。***•设计新的抗有丝分裂抗癌药物：更好地了解微管和配体之间的相互作用对于改进药物的设计至关重要。这些分子系统非常大。幸运的是，并非这些系统的所有部分都是平等的：重要的化学反应只发生在其中的一小部分，而其余部分只是形成了分子框架。在相互作用的分析中，我们将使用新的MCPs和片段分子轨道方法进行分子动力学模拟。***实现我们的目标将使hqp有机会创造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.