Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol.
Finding Chemical Reaction Paths with a Multilevel Preconditioning Protocol.
复制标题
使用多级预处理方案寻找化学反应路径。
DOI：
10.1021/ct500852y
复制
发表时间：
2014
影响因子：
5.5
通讯作者：
Dinner,AaronR
中科院分区：
文献类型：
--
作者：
Kale,Seyit;Sode,Olaseni;Weare,Jonathan;Dinner,AaronR
由于精确度所需的量子化学理论水平，寻找化学反应的过渡路径的计算成本可能很高。在这里，我们展示了最近引入的多级预适应方案(Tempkin等人，J.Chem。Phys.2014、140、184114)可以用来加速量子化学弦计算。我们通过为两个特征很好的反应：丙二醛的互变异构化和分支酸的Claissen重排反应找到最小能量路径来演示该方法。对于这些反应，我们证明了采用半经验方法的预条件密度泛函理论(DFT)将达到DFT下最优路径的计算成本降低了数倍。当热噪声可控时，该方法也显示出自由能计算的前景。
Finding transition paths for chemical reactions can be computationally costly owing to the level of quantum-chemical theory needed for accuracy. Here, we show that a multilevel preconditioning scheme that was recently introduced (Tempkin et al.J. Chem. Phys.2014,140, 184114) can be used to accelerate quantum-chemical string calculations. We demonstrate the method by finding minimum-energy paths for two well-characterized reactions: tautomerization of malonaldehyde and Claissen rearrangement of chorismate to prephanate. For these reactions, we show that preconditioning density functional theory (DFT) with a semiempirical method reduces the computational cost for reaching a converged path that is an optimum under DFT by several fold. The approach also shows promise for free energy calculations when thermal noise can be controlled.