arXiv:2512.07329physics.chem-phcond-mat.mtrl-sci2025-12被引 3

用二维RMSD投影可视化反应路径,更清晰展示结构变化与能量关系。

Two-dimensional RMSD projections for reaction path visualization and validation

  • 基于反应物/产物的校正RMSD构建二维投影平面。
  • 结合高斯过程插值能量面,支持区域由方差轮廓界定。
  • 适用于复杂反应路径验证,适合计算化学研究者参考。

过渡态或最低能量路径搜索是计算化学中的常规方法。传统分析将轨迹以相对能量对累积位移或图像序号作图,这类降维方式会掩盖高维结构演变,且具有历史依赖性,难以比较不同方法的优化过程,仅能对比计算次数、耗时和最终鞍点构型。本文提出一种新方法:将轨迹映射到由反应物与产物构型经排列校正的均方根偏差(RMSD)定义的二维平面上。能量通过梯度增强的高斯过程插值生成颜色映射表面,使用反多二次核,后验方差轮廓可区分数据支持区域与外推区域。旋转坐标系将RMSD平面分解为反应进度与垂直距离分量。在环加成反应中,机器学习势能面得到的鞍点与密度泛函理论参考结果位于相近能量等值线,尽管几何位移存在差异;该可视化框架还成功应用于更复杂的格氏重排与对旋双环丁烷开环反应,验证其有效性。

原文摘要 · Abstract (English)

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 are often 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.

反应路径可视化计算化学

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