Assessing the importance of multireference correlation in predicting reversed conductance decay
Assessing the importance of multireference correlation in predicting reversed conductance decay
复制标题
评估多参考相关性在预测反向电导衰减中的重要性
DOI：
10.1039/d3cp01110k
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发表时间：
2024
影响因子：
3.3
通讯作者：
Hoy, Erik P.
中科院分区：
文献类型：
--
作者：
Cossaboon, Tanner A.;Kazmi, Samir;Tineo, Matthew;Hoy, Erik P.
在经典的电子电阻器中，根据欧姆定律，电导随着器件长度的增加而衰减。虽然大多数分子系列的电导率随着分子长度的增加呈指数衰减，但存在一类单分子器件系列，其电导率反而随着分子/器件长度的增加而增加，这种现象称为反向电导率衰减。虽然电导衰减的逆转已经在理论上被反复预测，但它们在实验上要证明要困难得多。先前的研究表明，理论上的多参考文献（静态）相关误差可能是导致这种差异的主要原因，但大多数单分子运输方法无法处理多参考文献相关。利用我们独特的基于非平衡格林函数和多构型对密度泛函理论（NEGF-MCPDFT）的多参考输运方法，我们研究了先前预测的苯环线性链具有不同长度和电极设计的系统的反向电导衰减情况。我们将我们的NEGF- mcpdft结果与非多参考NEGF方法的结果进行比较，以量化静态相关在电导衰减逆转中的确切作用，并阐明它们在几何和电极设计/耦合考虑方面的相对重要性。
In a classical electronic resistor, conductance decays as the device length increases according to Ohm's Law. While most molecular series display a comparable exponential decay in conductance with increasing molecular length, a class of single-molecule device series exists where conductance instead increases with molecular/device length, a phenomenon called reversed conductance decay. While reversals of conductance decay have been repeatedly theoretically predicted, they have been far more difficult to demonstrate experimentally. Previous studies have suggested that theoretical multi-reference(static) correlation errors may be a major cause of this discrepancy, yet most single-molecule transport methods are unable to treat multireference correlation. Using our unique multireference transport method based on non-equilibrium Green's function and multiconfigurational pair-density functional theory (NEGF-MCPDFT), we examined a previously predicted case of reversed conductance decay in systems of linear chains of phenyl rings with varying lengths and electrode designs. We compare our NEGF-MCPDFT results to those of non-multireference NEGF methods to quantify the exact role of static correlation in conductance decay reversals and clarify their relative importance to geometric and electrode design/coupling considerations.