The Unified Reaction Valley Approach (URVA) explores a chemical reaction along the reaction path and the surrounding reaction valley, traced out by the reacting molecules on the potential energy surface from the early van der Waals region to the transition state and far out into the exit channel, where the products are located. A key feature of URVA is its focus on the curving of the reaction path. Moving along the reaction path, any electronic structure change of the reacting molecules is registered by a change in the normal vibrational modes perpendicular to the path, defining the reaction valley. This leads in turn to a change of the coupling between these modes with the large amplitude motion along the path. Since the couplings define the curvature of the reaction path, their change creates a unique curvature profile for each chemical reaction, the so-called fingerprint, with curvature minima Mn reflecting minimal change and curvature maxima Km, the locations of important chemical events such as bond breaking/forming, charge polarization and transfer, rehybridization, etc. The decomposition of the reaction path curvature into internal coordinate components provides a comprehensive insight into the origin and nature of all chemical changes taking place. Noteworthy is that even in complex reactions, e.g., reactions in enzymes, generally only a few components contribute to a certain chemical event. After summarizing the theoretical background of URVA, we discuss some recent applications including CN bond formation on Titan, gold catalysis, and a potential SARS-CoV-2 main protease inhibitor. We will also draw a connection between URVA and the quantum theory of atoms in molecules (QTAIM), exploring the famous Hohenberg/Kohn theorem. At the end of the talk the pURVA software is introduced.

Exploration of potential energy surfaces with the unified reaction valley approach

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