Rudolph A. Marcus

Bio: Rudolph A. Marcus is an academic researcher from California Institute of Technology. The author has contributed to research in topics: Semiclassical physics & Electron transfer. The author has an hindex of 91, co-authored 401 publications receiving 50560 citations. Previous affiliations of Rudolph A. Marcus include Claremont Colleges & Oak Ridge National Laboratory.

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I

Abstract: A mechanism for electron transfer reactions is described, in which there is very little spatial overlap of the electronic orbitals of the two reacting molecules in the activated complex. Assuming such a mechanism, a quantitative theory of the rates of oxidation‐reduction reactions involving electron transfer in solution is presented. The assumption of "slight‐overlap" is shown to lead to a reaction path which involves an intermediate state X* in which the electrical polarization of the solvent does not have the usual value appropriate for the given ionic charges (i.e., it does not have an equilibrium value). Using an equation developed elsewhere for the electrostatic free energy of nonequilibrium states, the free energy of all possible intermediate states is calculated. The characteristics of the most probable state are then determined with the aid of the calculus of variations by minimizing its free energy subject to certain restraints. A simple expression for the electrostatic contribution to the free energy of formation of the intermediate state from the reactants, ΔF*, is thereby obtained in terms of known quantities, such as ionic radii, charges, and the standard free energy of reaction. This intermediate state X* can either disappear to reform the reactants, or by an electronic jump mechanism to form a state X in which the ions are characteristic of the products. When the latter process is more probable than the former, the over‐all reaction rate is shown to be simply the rate of formation of the intermediate state, namely the collision number in solution multiplied by exp(—ΔF*/kT). Evidence in favor of this is cited. In a detailed quantitative comparison, given elsewhere, with the kinetic data, no arbitrary parameters are needed to obtain reasonable agreement of calculated and experimental results.

Chemical and Electrochemical Electron-Transfer Theory

Abstract: One of the active areas in reaction kinetics during the post-war years has been that of electron-transfer reactions. These reactions constitute one type of oxidation-reduction process and include both chemical and electrochemical systems. Many rate constants have now been measured (1-8) and they have stimulated a variety of theoretical studies (9-37). The field has been characterized by a strong interplay of theory and experiment, which now includes the testing of theoretically predicted quantitative correlations (34). Because of a certain unique feature of the purely electron-transfer reactions--the absence of bond rupture in the reaction step--these correlations are unusual. They do not have the arbitrary parameters that occur in theoretical studies of most other reactions in chemical kinetics. This review will be limited to purely electron transfer reactions.

Electron transfer reactions in chemistry. Theory and experiment

Abstract: Since the late 1940s, the field of electron transfer processes has grown enormously in chemistry, electrochemistry, and biology. The development of the field, experimentally and theoretically, as well as its relation to the study of the other kinds of chemical reactions, presents an intriguing history in which many threads have been brought together. In this article, some history, recent trends, and my own involvement are described.

On the Theory of Electron-Transfer Reactions. VI. Unified Treatment for Homogeneous and Electrode Reactions

Abstract: A unified theory of homogeneous and electrochemical electron‐transfer rates is developed using statistical mechanics. The treatment is a generalization of earlier papers of this series and is concerned with seeking a fairly broad basis for the quantitative correlations among chemical and electrochemical rate constants predicted in these earlier papers. The atomic motions inside the inner coordination shell of each reactant are treated as vibrations. The motions outside are treated by the "particle description," which emphasizes the functional dependence of potential energy and free energy on molecular properties and which avoids, thereby, some unnecessary assumptions about the molecular interactions.

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Abstract: 抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

Quantum mechanical continuum solvation models.

Abstract: 6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

Dye-Sensitized Solar Cells

Abstract: Dye-sensitized solar cells (DSCs) offer the possibilities to design solar cells with a large flexibility in shape, color, and transparency. DSC research groups have been established around the worl ...