Tuned Range-Separated Density Functional Theory and Dyson Orbital Formalism for Photoelectron Spectra,Journal of Chemical Theory and Computation

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Tuned Range-Separated Density Functional Theory and Dyson Orbital Formalism for Photoelectron Spectra
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2018-09-21 00:00:00 , DOI: 10.1021/acs.jctc.8b00707
T. Möhle ₁ , O. S. Bokareva _{1,

2} , G. Grell ₁ , O. Kühn ₁ , S. I. Bokarev ₁

Affiliation

Photoelectron spectroscopy represents a valuable tool to analyze structural and dynamical changes in molecular systems. Comprehensive interpretation of experimental data requires, however, involvement of reliable theoretical modeling. In this work, we present a protocol based on the combination of well-established linear-response time-dependent density functional theory and Dyson orbital formalism for the accurate prediction of both ionization energies and intensities. Essential here is the utilization of the optimally tuned range-separated hybrid density functionals, improving the ionization potentials not only of frontier but also of the deeper lying orbitals. In general, the protocol provides accurate results as illustrated by comparison to experiments for several gas-phase molecules, belonging to different classes. Further, we analyze possible pitfalls of this approach and, namely, discuss the ambiguities in the choice of optimal range-separation parameters, the influence of the stability of the ground state, and the spin contamination issues as possible sources of inaccuracies.

中文翻译：

调谐距离分离密度泛函理论和戴森轨道形式主义的光电子能谱

光电子能谱是分析分子系统结构和动力学变化的宝贵工具。但是，对实验数据的全面解释需要可靠的理论模型的参与。在这项工作中，我们提出了一个基于已建立的线性响应时间相关的密度泛函理论和戴森轨道形式主义相结合的协议，可准确预测电离能和强度。在这里，最重要的是利用优化调整的范围分隔的混合密度泛函，不仅提高边界的电离电势，而且提高深层轨道的电离电势。通常，该方案可提供准确的结果，如与属于不同类别的几种气相分子的实验进行比较所说明的。进一步，

更新日期：2018-09-21

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