Ethanol adsorption on the LaAlO3 (0 0 1) perovskite surface: A density functional theory study

• Ethanol adsorption on LaO-terminated LaAlO 3 (0 0 1) is studied using DFT with van der Waals corrections. • The most stable configuration involves ethanol binding through its oxygen atom to a surface La site. • Adsorption induces charge redistribution and strong polarization of the hydroxyl group. • The adjacent C–O bond is weakened as a result of adsorption-induced electronic effects. • NEB calculations show an activation barrier of ∼0.3 eV for O–H bond dissociation. Ethanol adsorption on the LaO-terminated LaAlO 3 (0 0 1) surface at low coverage was investigated using Density Functional Theory (DFT) with van der Waals (vdW) corrections. The most stable configuration involves ethanol binding through its oxygen atom to a surface La cation, with an adsorption energy of −2.2 eV and an equilibrium distance of 2.58 Å. The molecule remains strongly anchored to the substrate, and the analysis of the adsorption process points to a slight weakening of the C–O bond strengh, suggesting a potential starting point for surface-driven reaction pathways. Bond-order and structural analyses reveal La–O molecule and La–O surface bond lengths and bond orders of comparable magnitude, consistent with chemisorption. Adsorption also reduces the AlO–LaO interlayer spacing, reflecting charge redistribution within the perovskite lattice. The adsorption mechanism is further elucidated through complementary bond-order, bond-length, Bader-charge, and differential charge density analyses.