论文标题

使用内部坐标速度的最低能量途径和过渡状态的最初估计值

Initial estimate for minimum energy pathways and transition states using velocities in internal coordinates

论文作者

Palenik, Mark C

论文摘要

许多用于查找反应途径的算法需要对最小能量路径(MEP)的初始估计。大多数估计方法都使用差异方法,因此必须从更简单的路径(例如由笛卡尔插值产生的路径)中播种。通常,必须注意避免在此种子路径中的原子交叉点,并且估计量本身可能会融合到多个不良的局部最小值。作为替代方案,我们通过数值整合速度向量字段来形成初始估计,该速度向量场将从冗余内部坐标投射到笛卡尔流形中。我们将此方法与图像依赖对电位,测量方法和线性笛卡尔插值进行了比较:使用三个测试用例:乙烷中的甲基旋转,HCN $ \ \ $ HNC互变异分解,以及从二甲基硝胺中消除HONO。在第一个测试案例中,用我们的方法播种的零温度弦计算以比其他任何一个收敛的几何形状和SCF循环都明显少得多,而在第二个中,只有大地测量方法略高于我们的表现。在第三个测试案例中,我们将每个路径的中点用作过渡状态计算的初始猜测。我们的中点在几何上是最接近真实过渡状态的,并以最少的几何形状和SCF周期收敛。

Many algorithms for finding reaction pathways require an initial estimate of the minimum energy path (MEP). Most estimation methods use a variational approach and thus must be seeded from an even simpler path, such as one generated by Cartesian interpolation. Often, care must be taken to avoid atomic intersections in this seed path, and the estimator itself may potentially converge to multiple undesirable local minima. As an alternative we form an initial estimate by numerically integrating a velocity vector field that is projected from redundant internal coordinates into the Cartesian manifold. We compare this method to the image dependent pair potential, the geodesic method, and linear Cartesian interpolation using three test cases: the rotation of a methyl group in ethane, HCN$\to$HNC tautomerization, and HONO elimination from dimethylnitramine. In the first test case, a zero-temperature string calculation seeded with our method converges to the MEP in significantly fewer geometry and SCF cycles than any of the others, while in the second, only the geodesic method slightly outperformed ours. In the third test case, we used the midpoint of each path as an initial guess for a transition state calculation. Our midpoint was geometrically the closest to the true transition state and converged in the fewest geometry and SCF cycles.

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