title: 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.
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, USA.
authors.forename: Cui
authors.initials: C
authors.lastname: Zhang
authors.forename: Tuan Anh
authors.initials: TA
authors.lastname: Pham
authors.forename: François
authors.initials: F
authors.lastname: Gygi
authors.forename: Giulia
authors.initials: G
authors.lastname: Galli
mesh_terms: D000838:Anions / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry*; D004583:Electrons; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D012995:Solubility
chemical_list: D000838:Anions; D002712:Chlorides