论文标题
具有激发态平均场和扰动理论的核心激发
Core Excitations with Excited State Mean Field and Perturbation Theory
论文作者
论文摘要
我们测试激发态平均场理论的疗效及其激发状态特异性扰动理论对K边缘位置和X射线峰分离的预测。我们发现，平均场理论令人惊讶地准确，即使它不包含差异电子相关效应。在扰动理论中，我们测试了多个核心价分离方案，并发现，由于平均场理论已经如此准确，一种流行的分离方案中的电子计数偏见在预测k-edges时成为主要误差。令人高兴的是，这些似乎相对容易纠正，从而导致K-Edge位置的扰动理论比耦合的集群理论更低，并且更准确，并且具有限制性的开放式Shell Kohn Kohn Sham理论的最新高临界度。对于峰分离，我们的初步数据显示，激发状态平均场理论是异常准确的，但是需要更广泛的测试来查看其且其扰动理论与耦合的群集峰分离相比如何。
We test the efficacy of excited state mean field theory and its excited-state-specific perturbation theory on the prediction of K-edge positions and X-ray peak separations. We find that the mean field theory is surprisingly accurate, even though it contains no accounting of differential electron correlation effects. In the perturbation theory, we test multiple core-valence separation schemes and find that, with the mean field theory already so accurate, electron-counting biases in one popular separation scheme become a dominant error when predicting K-edges. Happily, these appear to be relatively easy to correct for, leading to a perturbation theory for K-edge positions that is lower scaling and more accurate than coupled cluster theory and competitive in accuracy with recent high-accuracy results from restricted open-shell Kohn Sham theory. For peak separations, our preliminary data show excited state mean field theory to be exceptionally accurate, but more extensive testing will be needed to see how it and its perturbation theory compare to coupled cluster peak separations more broadly.
