论文标题

伯特 - 盐盐形式主义的优缺点

Pros and Cons of the Bethe-Salpeter Formalism for Ground-State Energies

论文作者

Loos, Pierre-François, Scemama, Anthony, Duchemin, Ivan, Jacquemin, Denis, Blase, Xavier

论文摘要

多体绿色的函数$ GW $近似与伯特 - 钙板方程(BSE)形式主义的组合已证明是计算分子系统中计算垂直过渡能量和振荡器强度的时间依赖性密度功能理论(TD-DFT)的有希望的替代方法。 BSE形式主义也可以通过绝热连接波动定理(ACFDT)来计算地面相关能量。在这里,我们研究了其平衡键长度附近的几个双原子分子的地下势能表面(PE)的拓扑。多亏了与最先进的计算方法(CC3)的比较,我们表明ACFDT@bse非常准确,甚至可以就总能量和平衡键竞争,甚至可以与低阶耦合群集方法(CC2和CCSD)竞争。但是,有时我们会在识别几美元的$ GW $ quasiparticle能量时观察到地面PES上的非物理不规则性。

The combination of the many-body Green's function $GW$ approximation and the Bethe-Salpeter equation (BSE) formalism has shown to be a promising alternative to time-dependent density-functional theory (TD-DFT) for computing vertical transition energies and oscillator strengths in molecular systems. The BSE formalism can also be employed to compute ground-state correlation energies thanks to the adiabatic-connection fluctuation-dissipation theorem (ACFDT). Here, we study the topology of the ground-state potential energy surfaces (PES) of several diatomic molecules near their equilibrium bond length. Thanks to comparisons with state-of-art computational approaches (CC3), we show that ACFDT@BSE is surprisingly accurate, and can even compete with lower-order coupled cluster methods (CC2 and CCSD) in terms of total energies and equilibrium bond distances for the considered systems. However, we sometimes observe unphysical irregularities on the ground-state PES in relation with difficulties in the identification of a few $GW$ quasiparticle energies.

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