New theoretical methods for the exploration of functional landscapes

Molecular functionality can be often directly attributed to given properties of the electronic wavefunction. Analogous to the potential energy surface, these properties can be represented as a function of the nuclear coordinates, giving rise to molecular “functional landscapes.” However, so far there has been no possibility for their systematic investigation. This perspective aims to discuss the development of new theoretical methods based on the multistate extension of the metadynamics approach, employing electronic collective variables. This emerging methodology allows to explore functional landscapes and to gain a deeper understanding of the structure–function relation in molecules and complex molecular systems in the ground and excited electronic state. Molecular functionality can be attributed to properties of the electronic wavefunction. Analogous to the potential energy surface, these properties can be represented as a function of the nuclear coordinates, giving rise to “functional landscapes.” So far there has been no possibility for their systematic investigation. This perspective discusses new theoretical methods based on the multistate extension of the metadynamics, employing electronic collective variables, suitable to explore functional landscapes in the ground and excited electronic state.