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反称双幂次波函数中的大小一致性误差可以完全消除。

Size consistency error in the antisymmetric geminal power wave function can be completely removed.

机构信息

Department of Chemistry, University of California, Berkeley, California 94720, USA.

出版信息

Phys Rev Lett. 2012 Nov 16;109(20):203001. doi: 10.1103/PhysRevLett.109.203001. Epub 2012 Nov 12.

Abstract

The accurate but expensive product of geminals ansatz may be approximated by a geminal power, but this approach sacrifices size consistency. Here, we show both analytically and numerically that a size consistent form very similar to the product of geminals can be recovered using a network of location-specific Jastrow factors. Upon variational energy minimization, the network creates particle number projections that remove the charge fluctuations responsible for size inconsistency. This polynomial cost approach captures strong many-electron correlations, giving a maximum error of just 1.8 kcal/mol during the double-bond dissociation of H(2)O in an STO-3G atomic orbital basis.

摘要

双子算符方法的精确但昂贵的产物可以用双子幂来近似,但这种方法牺牲了大小一致性。在这里,我们通过分析和数值计算表明,可以使用位置特定的 Jastrow 因子网络来恢复与双子乘积非常相似的大小一致的形式。通过变分能量最小化,该网络创建了粒子数投影,消除了导致大小不一致的电荷涨落。这种多项式代价方法可以捕捉强多电子相关,在 STO-3G 原子轨道基下,H(2)O 的双键离解中,最大误差仅为 1.8 kcal/mol。

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