A FIRST SOLUTION, FOR LIH, OF A MOLECULAR TRANSCORRELATED WAVE EQUATION BY MEANS OF RESTRICTED NUMERICAL INTEGRATION
A FIRST SOLUTION, FOR LIH, OF A MOLECULAR TRANSCORRELATED WAVE EQUATION BY MEANS OF RESTRICTED NUMERICAL INTEGRATION
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DOI：
10.1098/rspa.1969.0120
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发表时间：
1969-01-01
影响因子：
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通讯作者：
HANDY, NC
中科院分区：
文献类型：
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作者：
BOYS, SF;HANDY, NC
通过求解适当的互关联波动方程（C-1HC-W）ε = 0，首次计算了LiH分子的波函数和能量。计算结果与Handy和Boys（1968 c）对Ne原子的高精度计算结果是雅阁的。球对称的Ne问题提供了这样的优势，积分几乎可以准确地评估。新的问题，评估这些积分的功能有关的许多核，现在已经克服了一个特定的数值积分程序，它提供了一个更高的精度比对应的准确性的能量积分为一个普通的积分。因此，可以使用一组在数量上比其他方法更受限制的点。每个电子的误差几乎小到键能的1%，并且可以合理地预期，对于广泛的分子和反应系统，这种方法的后续应用将很容易超过这种精度。该方法依赖于以适用于任何分子的方式将ri_j的函数直接引入相关因子，并且对于第一个分子的成功实施可以提供理论化学预测方法的转折点。整套程序的编制需要不到一个人年的时间，其一般特点是，这种方法比以前的方法简单得多，以前的方法似乎不能达到这种精度。
The first calculation of a molecular wavefunction and energy by the solution of the appropriate transcorrelated wave equation (C-1HC–W)ϕ = 0 has been made for LiH. The results are in accord with the high accuracy found for the Ne atom by Handy & Boys (1968c). The spherical symmetry of the Ne problem gave such advantages that the integrals could virtually be evaluated exactly. The new problem of evaluating these integrals for functions about the many nuclei has now been overcome by a particular numerical integration procedure which gives a much higher accuracy in the energy than corresponds to the accuracy of integration for an ordinary integral. Hence a set of points which is much more restricted in number than otherwise can be used. The error per electron is nearly as small as 1 % of a bond energy, and it is reasonable to expect that later applications of this method will easily surpass this accuracy for a wide range of molecules, and for reacting systems. The method depends on the direct introduction of functions ofrijinto the correlation factor in a way applicable to any molecule and the successful implementation of this for the first molecule may provide a turning point in methods of theoretical chemical prediction. The preparation of the whole set of programs requires less than one man year and the general characteristics are those of a method which is much simpler than the previous methods which do not appear capable of this level of accuracy.