Common Cations Are Not Polarizable: Effects of Dispersion Correction on Hydration Structures from Ab Initio Molecular Dynamics

0572234 - ÚOCHB 2024 RIV US eng J - Článek v odborném periodiku
Košťál, Vojtěch - Mason, Philip E. - Martinez-Seara, Hector - Jungwirth, Pavel
Common Cations Are Not Polarizable: Effects of Dispersion Correction on Hydration Structures from Ab Initio Molecular Dynamics.
Journal of Physical Chemistry Letters. Roč. 14, č. 19 (2023), s. 4403-4408. ISSN 1948-7185
Grant CEP: GA ČR(CZ) GX19-26854X
Institucionální podpora: RVO:61388963
Klíčová slova: generalized gradient approximation * density functional theory * accurate description
Obor OECD: Physical chemistry
Impakt faktor: 5.7, rok: 2022
Způsob publikování: Open access
https://doi.org/10.1021/acs.jpclett.3c00856

We employed density functional theory-based ab initio molecular dynamics simulations to examine the hydration structure of several common alkali and alkali earth metal cations. We found that the commonly used atom pairwise dispersion correction scheme D3, which assigns dispersion coefficients based on the neutral form of the atom rather than its actual oxidation state, leads to inaccuracies in the hydration structures of these cations. We evaluated this effect for lithium, sodium, potassium, and calcium and found that the inaccuracies are particularly pronounced for sodium and potassium compared to the experiment. To remedy this issue, we propose disabling the D3 correction specifically for all cation-including pairs, which leads to a much better agreement with experimental data.
Trvalý link: https://hdl.handle.net/11104/0342998