Real-space pseudopotential method for computing the vibrational Stark effect

Abstract

The vibrational Stark shift is an important effect in determining the electrostatic environment for molecular or condensed matter systems. However, accurate ab initio calculations of the vibrational Stark effect are a technically demanding challenge. In this paper, we make use of density functional theory constructed on a real-space grid to expedite the computation of this effect. Our format is especially advantageous for the investigation of small molecules in finite fields as cluster boundary conditions eliminate spurious supercell interactions and allow for charged systems, while convergence is controlled by a single parameter, the grid spacing. The Stark tuning rate is highly sensitive to the interaction between anharmonicity in a vibrational mode and the applied field. To ensure this subtle interaction is fully captured, we apply three parallel approaches: a direct finite field, a perturbative method, and a molecular dynamics method. Finally, we illustrate this method by applying it to several small molecules containing C–O and C–N bonds and show that a consistent result can be obtained.