Communication: Electronic structure of the solvated chloride anion from first principles molecular dynamics

Abstract

We present first principles molecular dynamics simulations of the chloride anion in liquid water performed using gradient-corrected and hybrid density functionals. We show that it is necessary to use hybrid functionals both for the generation of molecular dynamics trajectories and for the calculation of electronic states in order to obtain a qualitatively correct description of the electronic properties of the solution. In particular, it is only with hybrid functionals that the highest occupied molecular orbital of the anion is found above the valence band maximum of water, consistent with photoelectron detachment measurements. Similar results were obtained using many body perturbation theory within the G0W0 approximation. © 2013 AIP Publishing LLC.