Theoretical and Computational Chemistry

Classical Ab Initio Molecular Dynamics Run at an Elevated Temperature is Not a Good Model for the Nuclear Quantum Effects in Water at Ambient Temperature



It is a common practice in ab initio molecular dynamics (AIMD) simulations of water to use an elevated temperature to overcome the over-structuring and slow diffusion predicted by most current density functional theory (DFT) models. The simulation results obtained in this distinct thermodynamic ensemble are then compared with experimental data at ambient temperature based on the rationale that a higher temperature effectively recovers nuclear quantum effects (NQEs) that are missing in the classical AIMD simulations. In this work, we systematically examine the foundation of this assumption for several DFT models as well as for the many-body MB-pol model. We find for the cases studied that a higher temperature does not correctly mimic NQEs at room temperature, which is especially manifest in significantly different three-body correlations as well as dynamics. In many of these cases, the effects of NQEs are exactly the opposite of the effects of carrying out the simulations at an elevated temperature.


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