Theoretical Studies in Chemical Kinetics and Related Topics

加州理工学院的鲁道夫·马库斯在理论和计算化学计划的支持下，开展了关于臭氧形成、离子转移和电子转移领域的化学反应速率和相关问题的理论研究。我们将研究臭氧形成中与质量无关的不寻常的同位素效应，以及实验观察到的相关压力和温度效应。通过与现有的实验和计算机模拟的比较，我们将进一步发展最近关于离子在不混溶的液-液界面上迁移的理论，以及离子接近纳米和宏观表面的理论，使用奇异的流体动力学行为作为基准。最后，关于半导体/液体界面电子转移的工作将被扩展，目的是获得一个简单的局部解析或求积表达式。这将为检查现有的现象学模型提供基础，并使测试DNA、植物光系统和其他材料中的远程电子转移的微扰方法成为可能。所有这些理论研究都受到当前实验结果的推动。这一理论项目的成果预计将对几个科学和技术学科产生影响。同位素研究将改善对地球大气层和其他行星大气中的化学反应的洞察。随着对电化学过程更好的理解，纳米技术的进步有望实现。这项研究对电子器件的结构和对化学腐蚀的理解也有一定的意义。

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.