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A size extensive energy functional derived from a double configuration interaction approach: The role of N representability conditions

机译:从双重配置相互作用方法获得的尺寸广泛的能量泛函:N可表示性条件的作用

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Starting from a configuration interaction (CI) approach including only doubly excited configurations, the corresponding energy functional is modified by introduction of a topological factor in the normalization condition of the CI coefficients in such a way that it gets inherently size extensive. Constraints imposed by N representability conditions on the modified functional are discussed and lead to a specific choice of the topological factor. The basic variable in the modified energy functional is the second-order reduced density matrix parametrized in terms of CI-like coefficients. Test calculations for a variety of small molecules show that the numerical results obtained with the new functional are in very good agreement with those obtained from coupled cluster singles doubles calculations. (c) 2006 American Institute of Physics.
机译:从仅包含双激发构型的构型相互作用(CI)方法开始,通过在CI系数的归一化条件下引入拓扑因子来修改相应的能量功能,以使它固有地具有较大的尺寸。讨论了N个可表示性条件对修改后的功能施加的约束,并导致对拓扑因子的特定选择。修改后的能量函数中的基本变量是根据类CI系数参数化的二阶降密度矩阵。对各种小分子的测试计算表明,使用新功能获得的数值结果与从耦合簇单重双数计算获得的数值结果非常吻合。 (c)2006年美国物理研究所。

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