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首页> 外文期刊>The Journal of Chemical Physics >Communication: Configuration interaction singles has a large systematic bias against charge-transfer states
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Communication: Configuration interaction singles has a large systematic bias against charge-transfer states

机译：交流：配置交互单打对电荷转移状态有较大的系统偏见

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摘要

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.
机译：我们显示，标准配置相互作用单分子（CIS）对电荷转移（CT）状态具有系统性偏见，其中与非CT状态相比，针对CT状态计算出的垂直激发能过高（不超过1 eV）。我们针对分子间和分子内电子转移的一系列化学问题，通过经验证明了这一偏差，然后，对于一个小的分析模型，我们证明了这种巨大的准确性差异源于必须伴随的电子结构的巨大变化远程电荷转移。迄今为止，这项研究得出的结论是，即使在波动函数理论的背景下，仅靠CIS仍不足以提供对激发态表面（CT和非CT）的平衡描述，并且必须包括显式的电子-电子相关性。另外（例如，通过CIS（D））用于电荷转移应用。

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