The development of new density functional based methods and their application to catalysis

催化作用是一种温和的艺术，无需高压或过热等强力手段即可触发理想的化学反应。它的实际应用已经改变了我们周围的世界，促进了各种合成材料的生产。大自然还利用其他催化剂将大气中的氮、氧和二氧化碳转化为对地球生态系统至关重要的化学物质。催化剂触发反应的具体方式通常不为人所知。由于催化过程是快速的，即使用复杂的实验检测方法也很难跟踪。幸运的是，计算机技术的快速发展与建模方法的重大进步相结合，开辟了通过计算机模拟分析催化过程的途径。本研究的目的是进一步探索这些可能性。本文采用密度泛函理论（DFT）作为理论模型。在过去的30年里，与阿姆斯特丹自由大学的E.J. Baerends教授的理论小组合作，开发了一个名为ADF（阿姆斯特丹密度泛函程序）的相当大的程序系统，用于在数字计算机上进行计算。长期目标是将ADF开发成用于化学、固体物理、生物和表面科学的多尺度模拟软件包。ADF目前在工业、政府和学术界有大约1000个用户。我们自己在未来5年的发展将需要一些方法，使涉及过渡金属中心的化学反应的研究更容易处理。与往年相比，我们将更加重视周期体系势能面上的反应。我们进一步参与了新理论的开发和实现，这将使使用基于dft的方法以高精度计算激发态特性成为可能。

Catalysis is the gentle art of triggering desirable chemical reactions without forceful means such as high pressures or excessive heat. Its practical use has changed the world around us by facilitating the production of an ever-increasing variety of synthetic materials. Other catalysts are employed by nature to convert nitrogen, oxygen and carbon dioxide from the atmosphere into chemicals vital to the ecosystem of our planet. The way in which reactions are triggered by catalysts is often not known in details. Because catalytic processes are fast, they are difficult to follow even by sophisticated experimental detection methods. Fortunately, the rapid developments in computer technology combined with significant advances in modeling methodologies have opened up ways in which catalytic processes can be analyzed by computer simulation. It is the objective of the proposed research to explore these possibilities further. We have adopted Density Functional Theory (DFT) as our theoretical model. A considerable program system called ADF (Amsterdam Density Functional program) has been developed over the past 30 years for calculations on digital computers in collaboration with the theory group of Professor E.J. Baerends at the Free University in Amsterdam. It is the long term goal to develop ADF into a multi-scale simulation package for use in chemistry, solid state physics, biology and surface science. ADF has currently some 1000 users in industry, government, and academia. Our own developments over the next 5 years will entail methodologies that can make the study of chemical reactions involving transition metal centers more tractable. In contrast to previous years, more emphasis will be given to reactions on the potential energy surface of periodic systems.We are further involved with the development and implementation of a new theory that should make it possible to calculate excited state properties with high accuracy using DFT-based methods.