Communication: configuration interaction singles has a large systematic bias against charge-transfer states.
Communication: configuration interaction singles has a large systematic bias against charge-transfer states.
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通信：构型相互作用单分子对电荷转移状态有很大的系统偏差。
DOI：
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发表时间：
2011
影响因子：
4.4
通讯作者：
Joseph E. Subotnik
中科院分区：
文献类型：
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作者：
Joseph E. Subotnik
我们发现标准组态相互作用单分子(CIS)对电荷转移(CT)态有系统的偏向，其中CT态的垂直激发能比非CT态高得不成比例(约1 eV)。我们在一系列分子间和分子内电子转移的化学问题上经验地证明了这种偏差，然后，对于一个小的分析模型，我们证明了这种精度上的巨大差异源于必须伴随着远程电荷转移的电子结构的巨大变化。到目前为止，这项研究的结论是，即使在波函数理论的背景下，单靠CIS也不足以提供对激发态表面(CT和非CT)的平衡描述，对于电荷转移应用，必须另外包括显式电子-电子关联(例如，通过CIS(D))。
We show that standard configuration interaction singles (CIS) has a systematic bias against charge-transfer (CT) states, wherein the computed vertical excitation energies for CT states are disproportionately too high (by >1 eV) as compared with non-CT states. We demonstrate this bias empirically for a set of chemical problems with both inter- and intra-molecular electron transfer, and then, for a small analytical model, we prove that this large difference in accuracy stems from the massive changes in electronic structure that must accompany long-range charge transfer. Thus far, the conclusion from this research is that, even in the context of wave function theory, CIS alone is insufficient for offering a balanced description of excited state surfaces (both CT and non-CT) and explicit electron-electron correlation must be included additionally (e.g., via CIS(D)) for charge-transfer applications.
影响因子：
4.4
作者：
Henderson, Thomas M.;Janesko, Benjamin G.;Scuseria, Gustavo E.
通讯作者：
Scuseria, Gustavo E.