The application of mathematical programming in theoretical chemistry. I. Saddle-point-search method applied to a H3 molecule.
The application of mathematical programming in theoretical chemistry. I. Saddle-point-search method applied to a H3 molecule.
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数学规划在理论化学中的应用。
DOI：
10.1246/bcsj.51.2472
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发表时间：
1978
期刊：
影响因子：
--
通讯作者：
Y. Yoneda
中科院分区：
文献类型：
--
作者：
Y. Yoneda
A new method to find the activated state of a reaction without preparing its potential energy surface was proposed and proved useful with the example of a H3 molecule. The first and the second derivatives of the total energy, with respect to every cartesian coordinate of a H3 molecule, were calculated by means of a perturbation method employing a modified EHMO. First, the bottom of the valley in the potential energy surface leading to the saddle point is sought with the aid of the quadratic approximation on the superplane on which the maximum curvature at the representative point lies. Second, the ascending path is determined to be the reverse of the steepest decending path according to the principle of microscopic reversibility. By repeating these procedures, the activated state was found without preparing the potential energy surface. The classical activation energy thus found was 8.8 kcal/ mol, which is in good agreement with the experimental values.
