Molecular Electronic Structure Theory: Methods and Applications

在这个由理论和计算化学项目支持的项目中，乔治亚大学的谢弗教授将继续他对原子和分子的电子结构以及它们所经历的反应的研究。研究方案由两部分组成。第一个是新方法的开发和测试，第二个是将这些方法应用于相关和有趣的化学问题。待开发的方法都旨在更准确地描述描述分子的势能面，以及分子变形和反应发生时能量的变化。在此授权期间，将特别关注适用于开壳物种的耦合簇方法的实施。此外，Schaefer将研究另一种电子相关方法的近似，即二阶构型相互作用。在此拨款期间，还将研究若干化学品的申请。这些项目的部分清单包括：详细检查苯基卡宾/三吡啶势能面；氨二聚体的平衡几何；配合物Fe2(CO)9中直接铁-铁键的研究。进一步的研究还将探讨混合密度泛函理论Hartree-Fock方法是否可以解决C20H20热化学中分子力学与实验之间的明显不一致。

In this project, which is supported by the Theoretical and Computational chemistry program, professor Schaefer at the University of Georgia will continue his investigations of the electronic structure of atoms and molecules and the reactions which they undergo. The research program is composed of two parts. The first is the development and testing of new methods, while the second is the application of these methods to relevant and interesting chemical problems. The methods to be developed are all aimed at a more accurate description of the potential energy surface(s) which describe a molecule and the energy changes once the molecule is distorted and reaction occurs. Of particular focus in this granting period will be an implementation of coupled cluster methods applicable to open shell species. Additionally Schaefer will investigate approximations to another electron-correlation method, namely second-order configuration interaction. During this grant period a number of chemical applications will also be pursed. A partial list of these projects includes: a detailed examination of the phenylcarbene/tropylidene potential energy surface; the equilibrium geometry of the ammonia dimer; an investigation of a direct iron-iron bond in the complex Fe2(CO)9. Further investigations will also probe whether hybrid density functional theory Hartree-Fock methods can resolve the apparent inconsistencies between molecular mechanics and experiment for the thermochemistry of C20H20.