Theoretical Studies in Chemical Kinetics and Related Topics

加州理工学院的Rudolph Marcus在理论与计算化学计划的支持下，开展臭氧形成、离子转移和电子转移等领域的化学反应速率及相关问题的理论研究。 将研究臭氧形成过程中不寻常的与质量无关的同位素效应，沿着相关的实验观察到的压力和温度效应的现象。最近的理论，离子转移通过不混溶的液-液界面将进一步发展，沿着理论的方法的离子纳米和宏观表面，使用奇异的流体动力学行为作为基准与现有的实验和计算机模拟比较。 最后，在半导体/液体界面上的电子转移的工作将得到扩展，目的是获得一个简单的本地解析或正交表达式。 这将提供一个基础，检查现有的现象学模型，并使测试的微扰方法在DNA，植物光系统，和其他材料的远程电子转移。 所有这些理论研究都是由当前的实验结果所激发的。这个理论项目的成果预计将影响几个科学和技术学科。同位素研究将有助于更好地了解地球大气和其他行星大气中的化学反应。 随着对电化学过程的理解的提高，预计纳米技术将取得进展。 这项研究也对电子设备的结构和化学腐蚀的理解有影响。

Rudolph Marcus of the California Institute of Technology is supported by the Theoretical and Computational Chemistry Program to carry out theoretical research on chemical reaction rates and related problems in the areas of ozone formation, ion transfer, and electron transfer. The unusual mass-independent isotope effect in ozone formation will be investigated, along with related experimentally observed pressure and temperature effects of the phenomenon. The recent theory of ion transfer across immiscible liquid-liquid interfaces will be further developed, along with theory for the approach of an ion to nano- and macro-surfaces, using the singular hydrodynamic behavior as a benchmark with comparison to available experiments and computer simulations. Finally, work on electron transfers at semiconductor/liquid interfaces will be extended with the aim of obtaining a simple local analytical or quadrature expression. This will provide a basis for examining existing phenomenological models, and enable testing of a perturbation approach for long-range electron transfer in DNA, plant photosystems, and other materials. All of these theoretical studies are motivated by current experimental results. The outcomes from this theoretical project are expected to impact several scientific and technological disciplines. The isotope studies will lead to improved insights into chemical reactions in the earth's atmosphere and other planetary atmospheres. Nanotechnology gains are expected with improved understanding of electrochemical processes. This research also has implications for electronic device construction and the understanding of chemical corrosion.