Erratum: Quantum Thermodynamics of Correlated-Catalytic State Conversion at Small Scale [Phys. Rev. Lett. 126, 150502...

Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.

Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in 1,5-hexadiene, referred to as...

The second law of thermodynamics can be stated in several different ways, and all of them can be shown to imply the others. The Clausius’ statement of the second law of thermodynamics is based on the irreversibility of spontaneous heat flow. It states that heat will not flow from the colder body to the hotter body unless some other process is involved. Additionally, as per the Kelvin’s statement, it is impossible to convert the heat from a single source into work without any other effect. This...

A thermodynamic process is a path through a sequence of states that takes a system from an initial state to a final state. In a cyclic process, the system returns to its initial state, so the changes in state properties and state functions (ΔT, Δp, ΔV, ΔU, ΔH) over one complete cycle are zero. However, heat and work transfers can still occur during the cycle, and the net heat and net work over the cycle need not be zero.A reversible process occurs when the system is infinitesimally close to...

The steady-state approximation, also referred to as the quasi-steady-state approximation to differentiate it from a true steady state, is a widely used method for simplifying calculations in complex reaction mechanisms. This approach is particularly useful when dealing with multi-step reactions that involve reverse reactions or several steps, which can significantly increase mathematical complexity and make the reactions nearly unsolvable analytically.The steady-state approximation operates on...

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...