Dyson orbitals within the fc-CVS-EOM-CCSD framework: theory and application to X-ray photoelectron spectroscopy of ground and excited states
Dyson orbitals within the fc-CVS-EOM-CCSD framework: theory and application to X-ray photoelectron spectroscopy of ground and excited states
复制标题
fc-CVS-EOM-CCSD 框架内的戴森轨道：基态和激发态 X 射线光电子能谱的理论与应用
DOI：
10.1039/c9cp03695d
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发表时间：
2020
影响因子：
3.3
通讯作者：
Coriani, Sonia
中科院分区：
文献类型：
--
作者：
Vidal, Marta L.;Krylov, Anna I.;Coriani, Sonia
我们报道了在最近引进的冷冻核(FC)核价态分离(CVS)运动方程(EOM)耦合团簇单双态(CCSD)方法中实现Dyson轨道的方法，该方法能够有效和可靠地表征核能级状态。FC-CVS-EOM-CCSD的电离势(IP)变体，其中EOM目标态比参考电子少一个电子，使得能够进入核心电离态，从而能够对X射线光电子能谱(XPS)及其时间分辨变体(TR-XPS)进行建模。戴森轨道是约化量，可以解释为抛射/附着的电子的关联态；它们进入各种实验上相关的量的表达式。在光电子能谱的背景下，戴森轨道可以用来估计光电离跃迁的强度。通过计算腺嘌呤基态的XPS和尿嘧啶激发态的Tr-XPS，说明了Dyson轨道和FC-CVS-EOM-IP-CCSD的实用性。
We report on the implementation of Dyson orbitals within the recently introduced frozen-core (fc) core–valence separated (CVS) equation-of-motion (EOM) coupled-cluster singles and doubles (CCSD) method, which enables efficient and reliable characterization of core-level states. The ionization potential (IP) variant of fc-CVS-EOM-CCSD, in which the EOM target states have one electron less than the reference, gives access to core-ionized states thus enabling modeling of X-ray photoelectron spectra (XPS) and its time-resolved variant (TR-XPS). Dyson orbitals are reduced quantities that can be interpreted as correlated states of the ejected/attached electron; they enter the expressions of various experimentally relevant quantities. In the context of photoelectron spectroscopy, Dyson orbitals can be used to estimate the strengths of photoionization transitions. We illustrate the utility of Dyson orbitals and fc-CVS-EOM-IP-CCSD by calculating XPS of the ground state of adenine and TR-XPS of the excited states of uracil.