Efficient Generation of Torsional Energy Profiles by Multifidelity Gaussian Processes for Hindered Rotor Corrections,Journal of Chemical Theory and Computation

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Efficient Generation of Torsional Energy Profiles by Multifidelity Gaussian Processes for Hindered Rotor Corrections
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-08-20 , DOI: 10.1021/acs.jctc.4c00475
Maximilian Fleck ₁ , Wassja A Kopp ₂ , Narasimhan Viswanathan ₂ , Niels Hansen ₁ , Joachim Gross ₁ , Kai Leonhard ₂

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Accurate thermochemistry computations often require proper treatment of torsional modes. The one-dimensional hindered rotor model has proven to be a computationally efficient solution, given a sufficiently accurate potential energy surface. Methods that provide potential energies at various compromises of uncertainty and computational time demand can be optimally combined within a multifidelity treatment. In this study, we demonstrate how multifidelity modeling leads to (1) smooth interpolation along low-fidelity scan points with uncertainty estimates, (2) inclusion of high-fidelity data that change the energetic order of conformations, and (3) predicting best next-point calculations to extend an initial coarse grid. Our diverse application set comprises molecules, clusters, and transition states of alcohols, ethers, and rings. We discuss limitations for cases in which the low-fidelity computation is highly unreliable. Different features of the potential energy curve affect different quantities. To obtain “optimal” fits, we apply strategies ranging from simple minimization of deviations to developing an acquisition function tailored for statistical thermodynamics. Bayesian prediction of best next calculations can save a substantial amount of computation time for one- and multidimensional hindered rotors.

中文翻译：

通过多保真高斯过程有效生成扭转能量轮廓以进行受阻转子校正

准确的热化学计算通常需要对扭转模式进行适当的处理。事实证明，只要有足够精确的势能面，一维受阻转子模型是一种计算高效的解决方案。在不确定性和计算时间需求的各种折衷下提供势能的方法可以在多保真处理中进行最佳组合。在本研究中，我们演示了多保真建模如何导致（1）沿着具有不确定性估计的低保真扫描点平滑插值，（2）包含改变构象能量顺序的高保真数据，以及（3）预测下一个最佳结果点计算以扩展初始粗网格。我们多样化的应用集包括醇、醚和环的分子、簇和过渡态。我们讨论低保真计算高度不可靠的情况的限制。势能曲线的不同特征影响不同的量。为了获得“最佳”拟合，我们应用了从简单的偏差最小化到开发适合统计热力学的采集函数等策略。对下一最佳计算的贝叶斯预测可以为一维和多维受阻转子节省大量计算时间。

更新日期：2024-08-20

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