论文标题
来自$ GW $计算的光电电子光谱
Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations
论文作者
论文摘要
早期的光电子光谱$ 3D- $过渡金属二氧化衣，sco $ _ {2}^ - $，tio $ _ {2}^ - $，vo $ _ {2}^ - $ _ {2}^ - $，cro $ $ _ {2}^ - $ _ {2}^ - $，mno $ $ $ _ {2}^ - {2}^ - $，sem sem sem and sem and sembotiated and dy and d. $ GW $近似中的扰动理论，使用一击扰动和特征值自洽形式主义。将不同水平的理论彼此比较，并与可用的光电子光谱进行了比较。 We show that one-shot $GW$ with a PBE0 starting point ($G_0W_0$@PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1-0.2 eV or less), which we attribute to the success of PBE0 in mitigating self-interaction error and providing good quasiparticle wave functions, which renders a first-order perturbative $GW$ correction effective. DFT起点（例如$ g_0w_0 $@pbe）在DFT起点中具有半局部性交换的一张$ GW $计算在预测电子去除能量方面的效果很差，而在1.5 ev接近1.5 ev的典型误差的情况下，可以预测电子删除能量。在DFT起点$ GW $的DFT起点中，较高量的精确交换（例如50％）与实验没有很好的一致性，这是通过与典型误差接近0.5 ev的过度结合轨道。 While not as accurate as $G_0W_0$@PBE0, the $G$-only eigenvalue self-consistent $GW$ scheme with $W$ fixed to the PBE level ($G_nW_0$@PBE) provides a reasonably predictive level of theory (typical errors near 0.3 eV) to describe photoelectron spectra of these $3d-$transition metal dioxide anions.另一方面，在$ w $（$ g_nw_n $@pbe）中添加特征值自隔离也使与实验的协议总体上加剧了。在我们先前关于其他过渡金属氧化物分子系统的研究的背景下，讨论了有关各种$ GW $方法的性能的发现。
Photoelectron spectra of early $3d-$transition metal dioxide anions, ScO$_{2}^-$, TiO$_{2}^-$, VO$_{2}^-$, CrO$_{2}^-$, MnO$_{2}^-$, are calculated using semilocal and hybrid density functional theory (DFT) and many-body perturbation theory within the $GW$ approximation using one-shot perturbative and eigenvalue self-consistent formalisms. Different levels of theory are compared with each other and with available photoelectron spectra. We show that one-shot $GW$ with a PBE0 starting point ($G_0W_0$@PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1-0.2 eV or less), which we attribute to the success of PBE0 in mitigating self-interaction error and providing good quasiparticle wave functions, which renders a first-order perturbative $GW$ correction effective. One-shot $GW$ calculations with semilocal exchange in the DFT starting point (e.g. $G_0W_0$@PBE) do poorly in predicting electron removal energies by underbinding orbitals with typical errors near 1.5 eV. Higher amounts of exact exchange (e.g. 50%) in the DFT starting point of one-shot $GW$ do not provide very good agreement with experiment by overbinding orbitals with typical errors near 0.5 eV. While not as accurate as $G_0W_0$@PBE0, the $G$-only eigenvalue self-consistent $GW$ scheme with $W$ fixed to the PBE level ($G_nW_0$@PBE) provides a reasonably predictive level of theory (typical errors near 0.3 eV) to describe photoelectron spectra of these $3d-$transition metal dioxide anions. Adding eigenvalue self-consistency also in $W$ ($G_nW_n$@PBE), on the other hand, worsens the agreement with experiment overall. Our findings on the performance of various $GW$ methods are discussed in the context of our previous studies on other transition metal oxide molecular systems.
