From free-energy profiles to activation free energies

Given a chemical reaction going from reactant (R) to the product (P) on a potential energy surface (PES) and a collective variable (CV) discriminating between R and P, we define the free-energy profile (FEP) as the logarithm of the marginal Boltzmann distribution of the CV. This FEP is not a true free energy. Nevertheless, it is common to treat the FEP as the free-energy analog of the minimum potential energy path and to take the activation free energy, Delta F-RP double dagger, as the difference between the maximum at the transition state and the minimum at R. We show that this approximation can result in large errors. The FEP depends on the CV and is, therefore, not unique. For the same reaction, different discriminating CVs can yield different. Delta F-RP double dagger. We derive an exact expression for the activation free energy that avoids this ambiguity. We find Delta F-RP double dagger to be a combination of the probability of the system being in the reactant state, the probability density on the dividing surface, and the thermal de Broglie wavelength associated with the transition. We apply our formalism to simple analytic models and realistic chemical systems and show that the FEP-based approximation applies only at low temperatures for CVs with a small effective mass. Most chemical reactions occur on complex, high-dimensional PES that cannot be treated analytically and pose the added challenge of choosing a good CV. We study the influence of that choice and find that, while the reaction free energy is largely unaffected, Delta F-RP double dagger is quite sensitive. (c) 2022 Author(s).

Automated summary

In this study, we investigated the calculation of activation free energy in chemical reactions and found that the approximation of the free-energy profile can lead to large errors. By defining a new exact expression, we identified an unambiguous method for calculating the activation free energy. The results suggest that this approach has practical value in dealing with high-dimensional potential energy surfaces and selecting appropriate variables.