On the ultrafast charge migration dynamics in isolated ionized halogen, chalcogen, pnicogen, and tetrel bonded clusters

Highlights: • Attosecond charge migration following ionization. • Halogen, chalcogen, pnicogen, and tetrel bonds. • Density functional theory. • Linear combination of atomic orbitals (LCAO). - Abstract: Here we demonstrate, compare and contrast relaxation- and correlation-driven charge migration dynamics in halogen, chalcogen, pnicogen and tetrel bonded clusters, following their vertical ionization. For this work, we have selected different isolated A–X:NH₃ clusters, where A represents F, Cl, CN and NH₂ substituents and X features Cl, SH, PH₂ and SiH₃ to exhibit specific noncovalent bonding interaction. The charge migration dynamics in these clusters is studied using the density functional theory (DFT) with the wB97XD functional and the 6-31+G(d,p) basis set. Approximately 400–600 attosecond time scale is predicted for charge migration in (1:1) AX:NH₃ complexes. Effects of basis set and intermolecular distance on the ultrafast charge migration dynamics through the halogen, chalcogen, pnicogen, and tetrel bonded clusters are also discussed. This is the first report on pure relaxation- and correlation-driven charge migration dynamics in chalcogen, pnicogen and tetrel bonded clusters.