Correlated Flat-Bottom Elastic Network Model for Improved Bond Rearrangement in Reaction Paths

用于改善反应路径中键重排的相关平底弹性网络模型

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Abstract

This study introduces correlated flat-bottom elastic network model (CFB-ENM), an extension of our recently developed flat-bottom elastic network model (FB-ENM) for generating plausible reaction paths, i.e., collision-free paths preserving nonreactive parts. While FB-ENM improved upon the widely used image-dependent pair potential (IDPP) by addressing unintended structural distortion and bond breaking, it still struggled with regulating the timing of series of bond breaking and formation. CFB-ENM overcomes this limitation by incorporating structure-based correlation terms. These terms impose constraints on pairs of atom pairs, ensuring immediate formation of new bonds after breaking of existing bonds. Using the direct MaxFlux method, we generated paths for 121 reactions involving main group elements and 35 reactions involving transition metals. We found that CFB-ENM significantly improves reaction paths compared to FB-ENM. CFB-ENM paths exhibited lower maximum DFT energies along the paths in most reactions, with nearly half showing significant energy reductions of several tens of kcal/mol. In the few cases where CFB-ENM yielded higher energy paths, most increases were below 10 kcal/mol. We also confirmed that CFB-ENM reduces computational costs in subsequent precise reaction path or transition state searches compared to FB-ENM. An implementation of CFB-ENM based on the Atomic Simulation Environment is available on GitHub for use in computational chemistry research.

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