2019/03/20 by Asmus Ougaard Doh, Doh, Asmus Ougaard, Daniele Selli +12
Materials Science · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #Copper-based nanomaterials and applications #FOS: Physical sciences #Gold and Silver Nanoparticles Synthesis and Applications #Materials Science (cond-mat.mtrl-sci) #Nonlinear Optical Materials Research #Spectroscopy and Quantum Chemical Studies
paper · pdf · doi:10.48550/arxiv.1903.08380
openalex publication_date 2019/03/20 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
Metal oxide nanoparticles (NPs) are regarded as good candidates for many\ntechnological applications, where their functional environment is often an\naqueous solution. The correct description of metal oxide electronic structure\nis still a challenge for local and semilocal density functionals, whereas\nhybrid functional methods provide an improved description, and local atomic\nfunction based codes such as CRYSTAL17 outperform plane wave codes when it\ncomes to hybrid functional calculations. However, the computational cost of\nhybrids are still prohibitive for systems of real sizes, in a real environment.\nTherefore, we here present and critically assess the accuracy of our\nelectrostatic embedding quantum mechanical/molecular mechanical (QM/MM)\ncoupling between CRYSTAL17 and AMBER16, and demonstrate some of its\ncapabilities via the case study of TiO2 NPs in water. First, we produced new\nLennard-Jones (LJ) parameters that improve the accuracy of water-water\ninteractions in the B3LYP/TIP3P coupling. Then, we applied our QM/MM coupling\nmethodology to describe the interaction of a 1 nm wide multilayer of water\nsurrounding a spherical TiO2 nanoparticle (NP). Optimizing the QM/MM water\nwater parameters was found to have little to no effect on the local NP\nproperties, which provide insights into the range of influence that can be\nattributed to the LJ term in the QM/MM coupling. The effect of adding\nadditional water in an MM fashion on the geometry optimized nanoparticle\nstructure is small, but more evident effects are seen in its electronic\nproperties. We also show that there is good transferability of existing QM/MM\nLJ parameters for organic molecules water interactions to our QM/MM\nimplementation, even though these parameters were obtained with a different QM\ncode and QM/MM implementation, but with the same functional.\n