Kim Seung Soo, Rhee Young Min
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Korea.
Phys Chem Chem Phys. 2024 Mar 13;26(11):9021-9036. doi: 10.1039/d3cp05643k.
Interpolation of potential energy surfaces (PESs) can provide a practical route to performing molecular dynamics simulations with a reliability matching a high-level quantum chemical calculation. An obstacle to its widespread use is perhaps the lack of general and optimal interpolation settings that can be applied in a black-box manner for any given molecular system. How to set up the weights for interpolation is one such task, and we still need to diversify the approaches in order to treat various systems. Here, we develop a new interpolation weighting scheme, which allows us to choose the weighting coordinates in a system-specific manner, by amplifying the contribution from specific internal coordinates. The new weighting scheme with an appropriate selection of coordinates is proved to be effective in reducing the interpolation error along the reaction pathway. As a demonstration, we consider the photoactive yellow protein chromophore system, as it constitutes itself as an interesting target that bears long-standing questions related to excited-state dynamics inside protein environments. We build its two-state diabatic interpolated PES with the new weighting scheme. We indeed see the utility of our scheme by conducting nonadiabatic molecular dynamics simulations with the required semi-global PES based on a limited number of data points.
势能面（PESs）的插值可以提供一条实用途径，以进行可靠性与高级量子化学计算相匹配的分子动力学模拟。其广泛应用的一个障碍可能是缺乏能够以黑箱方式应用于任何给定分子系统的通用且最优的插值设置。如何设置插值权重就是这样一项任务，并且我们仍需要使方法多样化以处理各种系统。在此，我们开发了一种新的插值加权方案，通过放大特定内坐标的贡献，使我们能够以系统特定的方式选择加权坐标。事实证明，通过适当选择坐标的新加权方案在减少沿反应路径的插值误差方面是有效的。作为一个示例，我们考虑光活性黄色蛋白发色团系统，因为它本身就是一个有趣的目标，存在与蛋白质环境中激发态动力学相关的长期问题。我们用新的加权方案构建其两态非绝热插值PES。通过基于有限数量的数据点使用所需的半全局PES进行非绝热分子动力学模拟，我们确实看到了我们方案的效用。
