Two-dimensional RMSD projections for reaction path visualization and validation

用于反应路径可视化和验证的二维 RMSD 投影

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Abstract

Transition state or minimum energy path finding methods constitute a routine component of the computational chemistry toolkit. Standard analysis involves trajectories conventionally plotted in terms of the relative energy to the initial state against a cumulative displacement variable, or the image number. These dimensional reductions obscure structural rearrangements in high dimensions and may often be history dependent. This precludes the ability to compare optimization histories of different methods beyond the number of calculations, time taken, and final saddle geometry. We present a method mapping trajectories onto a two-dimensional projection defined by a permutation corrected root mean square deviation from the reactant and product configurations. Energy is represented as an interpolated color-mapped surface constructed from all optimization steps using a gradient-enhanced Gaussian Process with the inverse multiquadric kernel, whose posterior variance contours delineate data-supported regions from extrapolated ones. A rotated coordinate frame decomposes the RMSD plane into reaction progress and orthogonal distance. We show the utility of the framework on a cycloaddition reaction, where a machine-learned potential saddle and density functional theory reference lie on comparable energy contours despite geometric displacements, along with the ratification of the visualization for more complex reactions, a Grignard rearrangement, and a conrotatory bicyclobutane ring opening. • Dimensionality Reduction: Maps optimization histories onto a 2D plane defined by distance-to-reactant and distance-to-product. • Landscape reconstruction: Interpolates sparse optimization samples onto a continuous energy surface with data-driven smoothing to visualize basin topologies. • Validation: Facilitates the direct projection of reference electronic structure calculations onto landscapes generated by machine-learned interatomic potentials.

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