ACCURACY OF AH EQUILIBRIUM GEOMETRIES BY SINGLE DETERMINANT MOLECULAR-ORBITAL THEORY
ACCURACY OF AH EQUILIBRIUM GEOMETRIES BY SINGLE DETERMINANT MOLECULAR-ORBITAL THEORY
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DOI：
10.1080/00268977400100171
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发表时间：
1974-01-01
影响因子：
1.7
通讯作者：
POPLE, JA
中科院分区：
文献类型：
--
作者：
HARIHARAN, PC;POPLE, JA
用具有d-型极化函数(6-31G*)的分裂价壳基的简单能级OFAB初始分子轨道理论，预测了AHn分子和阳离子(A为碳、氮、氧或氟)的基态和某些低激发态的平衡几何构型。结果表明，在有更广泛的基的相应计算的情况下，结果接近于单行列式波函数的极限。与实验结果的比较也显示出很好的一致性，尽管系统地低估了高达3%的键长。对于没有实验数据的系统，结果提供了平衡几何的预测。
A simple level ofab initiomolecular orbital theory with a split-valence shell basis withd-type polarization functions (6–31G*) is used to predict equilibrium geometries for the ground and some low-lying excited states ofAHnmolecules and cations whereAis carbon, nitrogen, oxygen or fluorine. The results are shown to be close to the limit for single determinant wave functions in cases where corresponding computations with more extensive bases are available. Comparison with experimental results also shows good agreement although a systematic underestimation of bond lengths up to 3 per cent is evident. For systems where no experimental data are available, the results provide predictions of equilibrium geometry.