Theoretical Study on the Excited Dynamics of Solid Surfaces and Surface Adsorbates

固体表面及表面吸附物的激发动力学是光催化、光能转换、半导体制造等前沿科学中的一个新兴领域。近年来，人们致力于阐明表面激发动力学中的分子过程。这些过程的电子机制的澄清是非常重要的理解和设计特定的表面光过程。在本研究计划中，我们用量子化学方法研究了几个问题，不仅涉及金属表面，而且涉及金属配合物。它们被分为三类，即，(1)金属表面的催化活性，（2）表面吸附物的STM图像，和（3）金属络合物的激发态和光化学反应。在第一个主题中，研究了催化乙烯环氧化反应的银表面的催化活性。第二，为了模拟STM图像，我们将Barthel的微扰理论应用到分子轨道理论中。通过对金属配合物激发态的系统研究，发现了简并轨道间激发的一般规律。最后，对Pt和Ir配合物光化学反应的电子机制进行了研究。

Excited dynamics of solid surfaces and surface adsorbates is a newly developing field in an advanced science such as photocatalyst, light-energy conversion, and manufacture of semiconductor. Recently, much effor thas been devoted to clarify molecular processes in surface excited dynamics. Clarifications of the electronic mechanisms of these processes are very important for understanding and designing specific surface photoprocesses. In this research project, we have studied several subjects concerning not only metal surfaces but also metal complexes by quantum chemical methods. They are divided into three categories ; i.e., (1) Catalytic activities on metal surfaces, (2) STM images of surface adsorbates, and (3) Excited states and photochemical reactions of metal complexes. In the first subject, a catalytic activity of a silver surface, which catalyzes an epoxidation reaction of ethylene, has been investigated. Secondly, a perturbation theory of Bardeen is applied to a molecular orbital theory in order to simulate an STM image. Based on the systematic researches on the excited states of metal complexes, we have found a general rule for the excitations between degenerate orbitals. Finally, electronic mechanisms of the photochemical reactions of Pt and Ir complexes are investigated.