论文标题
自由和mg孢子林的静态和动态相关性的平衡处理
A balanced treatment of static and dynamic correlation in free- and Mg-porphyrin
论文作者
论文摘要
我们提出了自由和MG-porphyrin的AB-INITIO动力构型相互作用（DCI）研究。 DCI是一种基于Löwdin降折叠技术的最近开发的活动空间理论。在活动空间中，通过完整的配置相互作用准确地描述了静态相关性。在高能，动态相关的子空间中，我们以$ GW $ GW $的功能理论近似在准粒子水平上处理相关性。最终理论结合了波浪函数和绿色的功能方法，以平衡静态和动态相关性的描述。该理论和算法给出了低计算成本的地面和激发态的多余处理。卟啉的四个轨道gouterman模型在大型相关的系统中提供了理想的活动空间，以测试大型系统嵌入的成本和准确性。我们在最小的四级活动空间中的无参数，完全的Ab-Initio DCI计算与实验和更昂贵的基准理论相吻合，$ q_x $和$ q_y $ $ $ $ $ $ $ $ $ q_y $ $ $ $ $ q_y $ $ $ $ $ $ q_y $ $ $ $ $ $。研究激发能的收敛性表明，DCI正确捕获了大小的广泛相关效应，这使其成为大型，密切相关的系统的有希望的活动空间理论。
We present an ab-initio dynamical configuration interaction (DCI) study of free- and Mg-porphyrin. DCI is a recently developed active space theory based on the Löwdin downfolding technique. In the active space, static correlation is described exactly with full configuration interaction. In the high energy, dynamically correlated subspace, we treat correlation at the quasiparticle level in the $GW$ approximation of Green's function theory. The final theory combines wave function and Green's function methods to give a balanced description of static and dynamic correlation. The theory and algorithm give a multireference treatment of ground and excited states for low computational cost. The four orbital Gouterman model of porphyrin offers an ideal active space in a large, correlated system to test the cost and accuracy of the embedding for large systems. Our parameter free, fully ab-initio DCI calculations in the minimal four-level active space agree well with both experiment and more expensive benchmark theories for the $Q_x$ and $Q_y$ transitions of free- and Mg-porphyrin. Studying the convergence of the excitation energies suggests that DCI correctly captures size extensive correlation effects, making it a promising active space theory for large, strongly-correlated systems.
