Molecular propensity as a driver for explorative reactivity studies

TL;DR

This paper introduces the concept of molecular propensity to predict a molecule's likelihood to react across different electronic states, enhancing the exploration of reaction mechanisms in quantum chemical studies.

Contribution

The authors develop a real-time quantum chemistry algorithm to detect molecular propensity, addressing limitations of traditional methods that require extensive parameter variation.

Findings

Algorithm successfully alerts to molecular propensity in real-time

Enhances detection of reaction pathways involving electronic state crossings

Improves reliability of reactivity studies by identifying predispositions

Abstract

Quantum chemical studies of reactivity involve calculations on a large number of molecular structures and comparison of their energies. Already the set-up of these calculations limits the scope of the results that one will obtain, because several system-specific variables such as the charge and spin need to be set prior to the calculation. For a reliable exploration of reaction mechanisms, a considerable number of calculations with varying global parameters must be taken into account, or important facts about the reactivity of the system under consideration can go undetected. For example, one could miss crossings of potential energy surfaces for different spin states or might not note that a molecule is prone to oxidation. Here, we introduce the concept of molecular propensity to account for the predisposition of a molecular system to react across different electronic states in certain nuclear configurations. Within our real-time quantum chemistry framework, we developed an algorithm that allows us to be alerted to such a propensity of a system under consideration.