Savino Longo

The ionization of the hydrogen atom confined in a spherical potential well and subjected to a static electric field is studied, using the diffusion Monte Carlo (DMC) method. Atomic ionization within a potential well is found to be a stationary, gradual, and reversible process. The value of the electric field at the onset of ionization is of the order of 0.1 atomic units, and depends on the symmetry of the atomic wave function and on the confinement dimension. By decreasing the confinement sphere, the difference between the bound and ionized states disappears, showing that strict confinement leads to pressure ionization of the atom. The off‐center case is studied characterizing the potential energy surface (PES), and the transition between field‐induced and pressure‐induced ionization is confirmed. Except for very weak fields, the minimum of the PES is reached when the proton is in contact with the boundary of the well.