A CONDITION TO REMOVE INDETERMINACY IN INTERELECTRONIC CORRELATION FUNCTIONS
A CONDITION TO REMOVE INDETERMINACY IN INTERELECTRONIC CORRELATION FUNCTIONS
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DOI：
10.1098/rspa.1969.0038
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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
很容易看出，有无数种不同的方法来表示由斯莱特行列式乘以两电子相关函数组成的相关波函数。它表明，它是可能的，引入一个额外的条件，不影响波函数，但导致的相关因子有最小的影响斯莱特行列式。这里提出的这种收缩条件的形式，只涉及六维积分，并已被发现，给一个非常系统的程序，在一个相关的波函数的氖彻底计算。可以定义某些相关展开函数，使得这些函数的任何组合给出满足该收缩条件的函数。这种压缩形式提供了相关函数和轨道的正则表达式，因此，如果在这种形式下进行两种不同的计算，就有可能比较两种相关函数和两组轨道，因为在完全精确的波函数中，它们应该是相同的。这种性质在以前的计算或理论中没有出现过。
It can easily be seen that there is an infinity of different ways of expressing a correlated wavefunction which consists of a Slater determinant multiplied by two-electron correlation functions. It is shown that it is possible to introduce an extra condition which does not affect the wavefunction but which causes the correlation factors to have the least effect on the Slater determinant. Here such a contraction condition is proposed in a form which only involves six-dimensional integrals and which has been found to give a very systematic procedure in a thorough calculation of a correlated wavefunction for neon. Certain correlation expansion functions can be defined so that any combination of these gives a function which satisfies this contraction condition. This contracted form provides canonical expressions for the correlation function and the orbitals so that if two different calculations are made in this form it is possible to compare the two correlation functions and the two sets of orbitals because in the completely accurate wavefunction they should be the same. Such a property has not occurred in previous calculations or theories.