Simultaneous computation of free energies and kinetics of rare events

Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...

The free energy change for a reaction that occurs under the standard conditions of 1 bar pressure and at 298 K is called the standard free energy change. Since free energy is a state function, its value depends only on the conditions of the initial and final states of the system. A convenient and common approach to the calculation of free energy changes for physical and chemical reactions is by use of widely available compilations of standard state thermodynamic data. One method involves the...

Transition-state theory, also known as activated-complex theory, provides a molecular-level explanation of reaction rates in both gas-phase and solution-phase reactions. It extends earlier kinetic models by considering the formation of a short-lived, high-energy configuration during a reaction.The progress of a chemical reaction can be represented using a reaction profile, which plots potential energy against the reaction coordinate. As two reactant molecules approach one another, their...

Fast reactions occurring in times shorter than the time needed to mix reactants pose a unique challenge for investigation. In a liquid-phase continuous-flow system, reactants A and B are swiftly pushed into the mixing chamber, where mixing occurs within 1 ms. The reaction mixture then flows through an observation tube, and one measures light absorption to determine species concentrations at various points of the tube. This method is most appropriate when relatively large volumes of reactants...

Eliminating drugs from the body is a vital process that occurs through excretion or metabolism. Understanding the kinetics of drug elimination is crucial for drug development, dosage determination, and optimizing patient outcomes.
Drug clearance depends on the rate of drug elimination and its plasma concentration. Another important parameter is a drug's half-life, which is the time required for its concentration to decrease by half. In most cases, drug clearance follows first-order kinetics,...

Reversible or opposing reactions play a crucial role in understanding the dynamic nature of chemical processes. While kinetics focuses on how reactions proceed, thermodynamics emphasizes that most reactions do not reach completion. Instead, a reverse reaction starts occurring over time, and when its rate equals that of the forward reaction, a dynamic equilibrium is established.For example, consider a simple chemical process where A forms B reversibly. The rate constants for the forward and...