A New Kinetic Theoritic Equation To Replace Marcus Theory

Marcus theory was initially proposed by Rudolph A. Marcusin1956on the basis of Libby’s idea on the electron transfer reactions in solutionusing the continuous medium theory and theclassical electrostatic mechanics according to the two-sphere model to describe the kinetics of the outer-sphere electron transfer reactions in solution. After developed by quantum theory and computer technique, Marcus theory has received extensive applications invarious fields, such as inorganic chemistry, organic chemistry, analytical chemistry, materials chemistry, energy chemistry, biochemistry, photochemistry, solution chemistry and so on. Meanwhile, the research object of Marcus theory has extended from the outer-sphere electron transfer reactions to the inner-sphere electron transfer reactions, even the nucleus transfer reactions, such as proton transfer reactions, hydrogen transfer reactions, hydride transfer reactions, atom-group transfer reactions, cyclization reactions and so on. Because Marcus theory directly conflicts with the law of conservation of energy and is fundamental error in principle, it is a urgent task to establish a new kinetic theoritic equation to replace it.In present work,based on the failure of Marcus theory and according tothe principles of transition state theory andMorse energy curve,a new kinetic theoriticequation was setablished to replace Marcus equation, In order to verify the practicality and effectiveness of the equation, we synthesized187organic hydride compounds. Through the new kinetic equation, the rate constants of more than thirty thounds ofhydride transfer reactions can be accurately predicted. Since the new kinetic equation is formally the same as the thermodynamic equation, we alsoachievedtheir perfect unity in form. Because there was no restrictionon the type of reactionswhen the new kinetic equation was established, in principle itcan be applied to any type of chemical reaction.We also proposedtwo new kinetic conceptions:the bond activation energy[ΔG≠H-D(XH)] of hydride donors in hydride self-exchange reaction and the bond formation energies [AG≠H-A(X+)]of hydride acceptorsin hydride self-exchange reactionand further established corresponding parameter database for187hydride compounds.