A Quantum-Mechanical Equation of Reaction Rates

Sidney Golden

R. Paul, G.N. Fowler, W. G. Laidlaw

Starting from a field theoretical representation of chemical reactions, the rate equation is developed in terms of the quantum mechanical Green's functions. The equation is valid for non-Markowian behavior and the approximations that are necessary in order to obtain the conventional (Markowian) rate equation are investigated. The effect of finite collision times is also discussed.

Kaitlin McCardle

Keisho Umesaki, Kei Odai

The reaction rate constant is defined as the rate at which a reactant annihilates or a product creates in a chemical reaction. The Hamiltonian of the reaction system describing elementary reactions has already been formulated by Miller et al（J. Chem. Phys. 1980, 72, 99-112） In addition, the reaction coordinates representing the progress of the reaction are also formulated by Fukui.（J. Phys. Chem. 1970, 74, 4161-4163） In the present paper, on the basis of these two theories, we first formulated the reaction rate constants of elementary reactions using classical statistical mechanics. Then we rewrited the rate constans quantum-mechanically according to the method of Wigner representations. By this rewriting, a correction term representing the quantum effect of the reaction rate constant was naturally derived.

Jiřı́ Pokorný, Tsu-Ming Wu

Jincheng Zhang

This paper introduces the concept of Quantum Chemical Friction (QCF), a novel framework for understanding and quantifying friction-like phenomena within molecular systems. Traditionally, friction has been defined within the context of macroscopic mechanics and solid-state interactions. However, this work proposes a fundamentally new approach, leveraging the principles of quantum mechanics to describe and model frictional resistance arising from the dynamics of electrons within molecular orbitals. We posit that electron movement, specifically the interference and decoherence of wavefunctions within specific orbital layers, directly contributes to what we term Quantum Chemical Friction. This concept is presented as a new mechanism affecting reaction rates and transition states, and it fundamentally alters our understanding of chemical kinetics. The theoretical framework utilizes a modified Schrödinger equation to incorporate orbital layer-specific frictional coefficients, providing a quantitative approach to predicting and controlling frictional effects in chemical reactions. The primary goal is to redefine reaction rates based on this QCF principle, offering a more accurate and nuanced depiction of chemical processes.