论文标题
扰动感知的局部相关方法的应用到耦合群集线性响应属性
Applications of a perturbation-aware local correlation method to coupled cluster linear response properties
论文作者
论文摘要
我们已经研究了两种新提出的对成对 - 天然轨道方法的变化的功效，以减少耦合群集属性计算的缩放。特别是，我们扩展了PNO ++和PNO ++组合方法的实现，这些方法利用现场感知的配对密度来定义用于描述电子相关效应的虚拟轨道空间，以测试其准确性，效率和鲁棒性在更大的分子系统上比以前研究过。 For fluoroalkane chains up to 1-fluoroheptane we find that the PNO++ and combined PNO++ methods yield smaller localization errors in response properties than PNO for similarly compact virtual spaces, and, while the PNO method performs better than the PNO++ method for correlation energies, the combined PNO++ method recovers similar accuracy for correlation energies to the PNO method.对于更多的三维分子结构，例如$α$ - 和$β-$ pinenes，PNO，PNO ++以及组合的PNO ++方法，所有响应属性都会产生相似的误差，而（$ S $）-1-苯基乙醇，PNO方法的性能稍好于其他两种方法。我们还研究了产品密度来定义虚拟空间的使用，以及两个定义弱对贡献的候选者。
We have investigated the efficacy of two recently proposed variations of the pair-natural-orbital approach to reducing the scaling of coupled cluster property calculations. In particular, we have extended our implementations of the PNO++ and combined PNO++ methods, which make use of field-aware pair-densities to define the virtual-orbital spaces used to describe electron correlation effects, in order to test their accuracy, efficiency, and robustness on larger molecular systems than previously investigated. For fluoroalkane chains up to 1-fluoroheptane we find that the PNO++ and combined PNO++ methods yield smaller localization errors in response properties than PNO for similarly compact virtual spaces, and, while the PNO method performs better than the PNO++ method for correlation energies, the combined PNO++ method recovers similar accuracy for correlation energies to the PNO method. For more three-dimensional molecular structures such as $α$- and $β-$pinenes, the PNO, PNO++, and combined PNO++ methods all yield similar errors for response properties, whereas for ($S$)-1-phenylethanol, the PNO method performs slightly better than the other two approaches. We also investigate the use of a product density to define the virtual space, as well as two candidates for defining weak-pair contributions.
