Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
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DOI：
10.1063/1.2104507
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发表时间：
2005-12-08
影响因子：
4.4
通讯作者：
Keil, FJ
中科院分区：
文献类型：
--
作者：
Heyden, A;Bell, AT;Keil, FJ
结合插值法和局部鞍点搜索算法可能是寻找化学反应过渡态的最有效方法。插值方法，如增长弦方法和轻推弹性带能够找到一个近似的最小能量途径，从而提供了一个很好的初始猜测的过渡态和虚模连接反应物和产品状态。由于插值方法通常只采用少量的配置和收敛缓慢接近最小能量途径，局部方法，如分区有理函数优化方法使用精确或近似的海森或最小模式的方法，如二聚体或Lanczos方法收敛到过渡态。提出了对[Henkelman和Jonnson J.Chem.Phys.111，7010（1999）]提出的原始二聚体方法的修改，将每个循环的梯度计算的数量从六个梯度减少到四个梯度或三个梯度和一个能量，并且显著提高了量子化学势能表面上的算法的整体性能，其中力受到数值噪声的影响。比较了二聚体方法和采用插值方法寻找过渡态的分区有理函数优化方法。24个不同的小型到中型的化学反应，涵盖了广泛的结构类型的结果表明，改进的二聚体方法是一个有效的替代鞍点搜索算法的中型到大型系统，往往甚至能够找到过渡态时，分区有理函数优化方法无法收敛。(c)2005年美国物理学会。
A combination of interpolation methods and local saddle-point search algorithms is probably the most efficient way of finding transition states in chemical reactions. Interpolation methods such as the growing-string method and the nudged-elastic band are able to find an approximation to the minimum-energy pathway and thereby provide a good initial guess for a transition state and imaginary mode connecting both reactant and product states. Since interpolation methods employ usually just a small number of configurations and converge slowly close to the minimum-energy pathway, local methods such as partitioned rational function optimization methods using either exact or approximate Hessians or minimum-mode-following methods such as the dimer or the Lanczos method have to be used to converge to the transition state. A modification to the original dimer method proposed by [Henkelman and Jonnson J. Chem. Phys. 111, 7010 (1999)] is presented, reducing the number of gradient calculations per cycle from six to four gradients or three gradients and one energy, and significantly improves the overall performance of the algorithm on quantum-chemical potential-energy surfaces, where forces are subject to numerical noise. A comparison is made between the dimer methods and the well-established partitioned rational function optimization methods for finding transition states after the use of interpolation methods. Results for 24 different small- to medium-sized chemical reactions covering a wide range of structural types demonstrate that the improved dimer method is an efficient alternative saddle-point search algorithm on medium-sized to large systems and is often even able to find transition states when partitioned rational function optimization methods fail to converge. (c) 2005 American Institute of Physics.