Reactive dynamics and spectroscopy of hydrogen transfer from neural network-based reactive potential energy surfaces
Year: 2020
Type: article
Abstract: The ‘in silico’ exploration of chemical, physical and biological systems requires accurate and efficient energy functions to follow their nuclear dynamics at a molecular and atomistic level. Recently, machine learning tools have gained a lot of attention in the field of molecular sciences and simulations and are increasingly used to investigate the dynamics of such systems. Among the various approaches, artificial neural networks (NNs) are one promising tool to learn a representation of potential energy surfaces. This is done by formulating the problem as a mapping from a set of atomic positions x and nuclear charges Z i to a potential energy V(x). Here, a fully-dimensional, reactive neural network representation for malonaldehyde (MA), acetoacetaldehyde (AAA) and acetylacetone (AcAc) is learned. It is used to run finite-temperature molecular dynamics simulations, and to determine the infrared spectra and the hydrogen transfer rates for the three molecules. The finite-temperature infrared spectrum for MA based on the NN learned on MP2 reference data provides a realistic representation of the low-frequency modes and the H-transfer band whereas the CH vibrations are somewhat too high in frequency. For AAA it is demonstrated that the IR spectroscopy is sensitive to the position of the transferring hydrogen at either the OCH- or OCCH3 end of the molecule. For the hydrogen transfer rates it is demonstrated that the O–O vibration (at ∼250 cm−1) is a gating mode and largely determines the rate at which the hydrogen is transferred between the donor and acceptor. Finally, possibilities to further improve such NN-based potential energy surfaces are explored. They include the transferability of an NN-learned energy function across chemical species (here methylation) and transfer learning from a lower level of reference data (MP2) to a higher level of theory (pair natural orbital-LCCSD(T)).
Source: New Journal of Physics
Authors: Silvan Käser, Oliver T Unke, Markus Meuwly
Institution: University of Basel
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $1,944
Awards: Intermolecular Interactions and the Role of Dynamics for Chemical Reactions in Complex Systems, Intermolecular interactions and the role of dynamics for chemical reactions in complex systems, G5599649393, Development of a Universal Neural Network-based Potential Energy Surface, G628552264, G993971353
OpenAlex ID: W2991242245