Optimization of diatomic state mixing in diatomics‐in‐molecules theory: The CHn potential‐energy surfaces
Optimization of diatomic state mixing in diatomics‐in‐molecules theory: The CHn potential‐energy surfaces
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双原子分子内理论中双原子状态混合的优化：CHn 势能面
DOI：
10.1063/1.432398
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发表时间：
1976
影响因子：
4.4
通讯作者：
C. Parr
中科院分区：
文献类型：
--
作者：
C. W. Eaker;C. Parr
将双原子分子（DIM）理论扩展到包括更大的价键（VB）基集和双原子VB结构之间混合的优化。这种混合对于DIM势能超表面（PEH）的计算至关重要，使用足够大的基集来产生给定对称性的多个双原子状态。为了与DIM的哲学保持一致，双原子状态混合被视为与分子中原子的数量无关。该方法用于计算CH2、CH3和CH4的基态和激发态势能。这些扩展的DIM结果证明了对早期DIM方法的许多改进，并且与从头算和实验结果很好地一致。
The diatomics‐in‐molecules (DIM) theory is extended to include larger valence bond (VB) basis sets and the optimization of mixing between the diatomic VB structures. This mixing is essential to the calculation of DIM potential‐energy hypersurfaces (PEH) using basis sets large enough to generate more than one diatomic state of a given symmetry. In keeping with the philosophy of DIM, the diatomic state mixing is treated as being independent of the number of atoms in the molecule. The method is used to calculate ground and excited state potential energies for CH2, CH3, and CH4. These extended DIM results demonstrate a number of improvements over earlier DIM methods and are in good agreement with ab initio and experimental results.