Adsorption of Zn(II) on two types of neutral (001) surfaces of kaolinite, tetrahedral Si(t) and octahedral Al(o), was studied by means of DFT calculations and classical molecular dynamics simulations. The position and structure for both outer-sphere and mono-/bi-dentate inner-sphere complexes of Zn(II) in aqueous environment were examined, with binding energy and radial distribution function calculated. Outer-sphere complex on the Si(t) surface, monodentate inner-sphere complex of "O-u" (surface oxygen with "upright" hydrogen) site and bidentate complex of "O-u-O-u" site of neighboring Al centers on the Al(o) surface are considered to be the dominant adsorption species. The outer-sphere complex is found six-coordinated with distorted octahedral geometry, while both the inner-sphere complexes exhibit the tetrahedral structure with coordination number of four. Hydrogen bonding interactions between oxygen or hydrogen of the kaolinite(001) surfaces and the aqua ligands of Zn(II) act as the key role for the structure and stability of adsorption complexes. Upon the Mulliken population analysis and partial density of states, both Zn(II) and surface oxygen accept electrons from aqua oxygens, and coupling of O 2p with the sp(3)d(2) or spa hybridization states of Zn(II) is the primary bonding nature of Zn(II) with oxygen in outer and inner-sphere complexes, respectively. (C) 2017 Elsevier B.V. All rights reserved.