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首页> 外文期刊>The Journal of Chemical Physics >Correlation-driven phenomena in periodic molecular systems from variational two-electron reduced density matrix theory
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Correlation-driven phenomena in periodic molecular systems from variational two-electron reduced density matrix theory

机译：分析二电子降低密度矩阵理论中周期分子系统中的相关驱动现象

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摘要

Correlation-driven phenomena in molecular periodic systems are challenging to predict computationally not only because such systems are periodically infinite but also because they are typically strongly correlated. Here, we generalize the variational two-electron reduced density matrix (2-RDM) theory to compute the energies and properties of strongly correlated periodic systems. The 2-RDM of the unit cell is directly computed subject to necessary N-representability conditions such that the unit-cell 2-RDM represents at least one N-electron density matrix. Two canonical but non-trivial systems, periodic metallic hydrogen chains and periodic acenes, are treated to demonstrate the methodology. We show that while single-reference correlation theories do not capture the strong (static) correlation effects in either of these molecular systems, the periodic variational 2-RDM theory predicts the Mott metal-to-insulator transition in the hydrogen chains and the length-dependent polyradical formation in acenes. For both hydrogen chains and acenes, the periodic calculations are compared with previous non-periodic calculations with the results showing a significant change in energies and increase in the electron correlation from the periodic boundary conditions. The 2-RDM theory, which allows for much larger active spaces than are traditionally possible, is applicable to studying correlation-driven phenomena in general periodic molecular solids and materials.
机译：分子周期系统中的关联驱动现象在计算上很难预测，不仅因为这类系统是周期无限的，而且因为它们通常是强关联的。在这里，我们推广了变分双电子约化密度矩阵（2-RDM）理论来计算强关联周期系统的能量和性质。根据必要的N-代表性条件直接计算单元的2-RDM，使得单元2-RDM代表至少一个N-电子密度矩阵。两个规范但非平凡的系统，周期性金属氢链和周期性乙炔，被用来演示该方法。我们发现，虽然单参考关联理论不能捕捉到这两个分子系统中的强（静态）关联效应，但周期变分2-RDM理论预测了氢链中的莫特金属-绝缘体转变和acenes中与长度相关的多自由基形成。对于氢链和乙炔，将周期性计算与之前的非周期性计算进行了比较，结果表明，从周期性边界条件来看，能量发生了显著变化，电子关联增加。2-RDM理论允许比传统可能大得多的活动空间，适用于研究一般周期性分子固体和材料中的关联驱动现象。

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