Tenorio Bruno Nunes Cabral, Decleva Piero, Coriani Sonia
DTU Chemistry - Department of Chemistry, Technical University of Denmark, Kemitorvet Bldg. 207, 2800 Kongens Lyngby, Denmark.
Istituto Officina dei Materiali IOM-CNR and Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, I-34121 Trieste, Italy.
J Chem Phys. 2021 Oct 7;155(13):131101. doi: 10.1063/5.0062130.
Double Core-Hole (DCH) states of small molecules are assessed with the restricted active space self-consistent field and multi-state restricted active space perturbation theory of second order approximations. To ensure an unbiased description of the relaxation and correlation effects on the DCH states, the neutral ground-state and DCH wave functions are optimized separately, whereas the spectral intensities are computed with a biorthonormalized set of molecular orbitals within the state-interaction approximation. Accurate shake-up satellite binding energies and intensities of double-core-ionized states (K) are obtained for HO, N, CO, and CH (n = 1-3). The results are analyzed in detail and show excellent agreement with recent theoretical and experimental data. The K shake-up spectra of HO and CH molecules are here completely characterized for the first time.
采用受限活性空间自洽场和二阶近似的多态受限活性空间微扰理论对小分子的双核空穴（DCH）态进行了评估。为确保对DCH态的弛豫和关联效应进行无偏描述，分别优化了中性基态和DCH波函数，而光谱强度则在态相互作用近似下用一组双正交分子轨道进行计算。获得了HO、N、CO和CH（n = 1 - 3）的双芯电离态（K）的准确振激卫星结合能和强度。对结果进行了详细分析，与最近的理论和实验数据显示出极好的一致性。首次完整地表征了HO和CH分子的K振激光谱。
