The Auger spectrum of benzene

Jayadev, Nayanthara Karippara; Ferino-Pérez, Anthuan; Matz, Florian; Krylov, Anna I.; Jagau, Thomas-C.

doi:10.1063/5.0138674

Cited by 8 publications

(34 citation statements)

References 117 publications

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“…We previously demonstrated that total and partial Auger decay widths can be extracted from CBF-EOMIP-CCSD wave functions of core-ionized states. [67][68][69] The decay is represented in these wave functions by 2h1p-excitations that fill the core hole. The resulting configurations give rise to the metastable character and are responsible for convergence problems when methods are used that do not treat the decay properly.…”

Section: Determination Of Auger Decay Widths With Complex-variable Me...mentioning

confidence: 99%

“…However, we recently showed that, even though the two approaches describe Auger decay in different ways, CBF-CCSD and Fano-EOM-CCSD agree well with each other about the Auger spectrum of benzene. 69…”

Section: Determination Of Auger Decay Widths With the Feshbach-fano M...mentioning

confidence: 99%

“…The easiest approach is to assign each EOMDIP-CCSD state to a single 2h configuration from the CBF-CCSD or CBF-EOMIP-CCSD calculation but this does not lead to convincing results. 69 Instead, a weighting procedure is necessary where each EOMDIP-CCSD state is assigned a combination of partial widths using the EOMDIP-CCSD amplitudes as weighing coefficients. This gives good results as we recently showed for the Auger spectrum of benzene.…”

Section: Mapping Between Auger Electron Energies and Decay Widthsmentioning

confidence: 99%

“…This gives good results as we recently showed for the Auger spectrum of benzene. 69 Here, we refine this approach by taking into account that the 2h character of the EOMDIP-CCSD states varies. Specifically, these states can have substantial contributions from 3h1p excitations that correspond to satellite states or do not represent Auger decay channels at all.…”

Section: Mapping Between Auger Electron Energies and Decay Widthsmentioning

confidence: 99%

“…The CBF approach is related to complex scaling 65,66 and has been shown to yield accurate total and partial Auger decay widths. [67][68][69] CBF methods are capable of describing the bound and unbound parts of a resonance state at once; there is no need to impose an explicit form for the wave function of the Auger electron.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio investigation of the Auger spectra of methane, ethane, ethylene, and acetylene

Matz

Nijssen

Jagau

2023

Preprint

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We present an ab initio computational study of the Auger spectra of methane, ethane, ethylene, and acetylene. Auger spectroscopy is a established technique to probe the electronic structure of molecules and exploits the Auger-Meitner effect that coreionized states produced by X-ray irradiation undergo. We compute partial decay widths for the relevant decay channels using coupled-cluster theory with single and double substitutions (CCSD) and equation-of-motion-CCSD theory combined with complex-scaled basis functions and Feshbach-Fano projection. We generate Auger spectra from these partial widths and draw conclusions about the strength of particular decay channels and trends between the four molecules. A connection to experimental results about fragmentation pathways of the electronic states produced by Auger decay is also made.

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Section: Determination Of Auger Decay Widths With Complex-variable Me...mentioning

confidence: 99%

Section: Determination Of Auger Decay Widths With the Feshbach-fano M...mentioning

confidence: 99%

Section: Mapping Between Auger Electron Energies and Decay Widthsmentioning

confidence: 99%

Section: Mapping Between Auger Electron Energies and Decay Widthsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ab initio investigation of the Auger spectra of methane, ethane, ethylene, and acetylene

Matz

Nijssen

Jagau

2023

Preprint

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State-Specific Coupled-Cluster Methods for Excited States

Damour,

Scemama,

Jacquemin

et al. 2024

J. Chem. Theory Comput.

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We reexamine ΔCCSD, a state-specific coupledcluster (CC) with single and double excitations (CCSD) approach that targets excited states through the utilization of non-Aufbau determinants. This methodology is particularly efficient when dealing with doubly excited states, a domain in which the standard equation-of-motion CCSD (EOM-CCSD) formalism falls short. Our goal here to evaluate the effectiveness of ΔCCSD when applied to other types of excited states, comparing its consistency and accuracy with EOM-CCSD. To this end, we report a benchmark on excitation energies computed with the ΔCCSD and EOM-CCSD methods for a set of molecular excited-state energies that encompasses not only doubly excited states but also doublet− doublet transitions and (singlet and triplet) singly excited states of closed-shell systems. In the latter case, we rely on a minimalist version of multireference CC known as the two-determinant CCSD method to compute the excited states. Our data set, consisting of 276 excited states stemming from the QUEST database [Veŕil et al., WIREs Comput. Mol. Sci. 2021, provides a significant base to draw general conclusions concerning the accuracy of ΔCCSD. Except for the doubly excited states, we found that ΔCCSD underperforms EOM-CCSD. For doublet−doublet transitions, the difference between the mean absolute errors (MAEs) of the two methodologies (of 0.10 and 0.07 eV) is less pronounced than that obtained for singly excited states of closed-shell systems (MAEs of 0.15 and 0.08 eV). This discrepancy is largely attributed to a greater number of excited states in the latter set exhibiting multiconfigurational characters, which are more challenging for ΔCCSD. We also found typically small improvements by employing state-specific optimized orbitals.

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Ab Initio Investigation of the Auger Spectra of Methane, Ethane, Ethylene, and Acetylene

2023

Self Cite

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We present an ab initio computational study of the Auger spectra of methane, ethane, ethylene, and acetylene. Auger spectroscopy is an established technique to probe the electronic structure of molecules and exploits the Auger–Meitner effect that core-ionized states undergo. We compute partial decay widths using coupled-cluster theory with single and double substitutions (CCSD) and equation-of-motion CCSD theory combined with complex-scaled basis functions and Feshbach–Fano projection. We generate Auger spectra from these partial widths and draw conclusions about the strength of particular decay channels and trends among the four molecules. A connection to experimental results about fragmentation pathways of the electronic states produced by Auger decay is also made.

show abstract

The Auger spectrum of benzene

Cited by 8 publications

References 117 publications

Ab initio investigation of the Auger spectra of methane, ethane, ethylene, and acetylene

Ab initio investigation of the Auger spectra of methane, ethane, ethylene, and acetylene

State-Specific Coupled-Cluster Methods for Excited States

Ab Initio Investigation of the Auger Spectra of Methane, Ethane, Ethylene, and Acetylene

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