Symmetry and reactivity of $\pi$-systems in electric and magnetic fields: a perspective from conceptual DFT

Abstract

[Abridged] The extension of conceptual DFT to include external fields in chemical systems is utilised to investigate the effects of strong magnetic fields on the electronic charge distribution and its consequences on the reactivity of $\pi$-systems. Formaldehyde, H$_2$CO, is considered as a prototypical example and current-DFT calculations are used to evaluate the electric dipole moment together with the electron density and the Fukui functions, which provide insight into how H$_2$CO behaves chemically in a magnetic field. In particular, the symmetries of these quantities are analysed based on group, representation, and corepresentation theories using QSym$^2$. This allows us to leverage the simple symmetry constraints on the macroscopic electric dipole moments to make profound predictions on the more nuanced symmetry transformation properties of the microscopic frontier MOs, electron densities, and Fukui functions. This is especially useful for complex-valued MOs in magnetic fields whose detailed symmetry analyses lead us to define the new concepts of modular and phasal symmetry breaking. Through these, the connection between the vanishing constraints on the electric dipole moments and the symmetry of electron densities and Fukui functions can be formalised, and the inability of the magnetic field in all three orientations considered to induce asymmetry with respect to the molecular plane can be understood from a molecular perspective. Furthermore, the detailed forms of the Fukui functions reveal remarkable reversals in the direction of the C=O dipole moment in the presence of a parallel or perpendicular magnetic field, which can be attributed to the mixing between frontier MOs due to their subduced symmetries in magnetic fields. The findings in this work are also discussed in the wider context of a long-standing debate on the possibility to create enantioselectivity by external fields.