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Title: Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra

Abstract

Green’s function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green’s function approach has been introduced, where the cumulant is obtained as the solution to a set of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green’s function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function associated with the core Green’s function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then obtained as a convolution of the core spectral function and an effective one-body absorption spectrum. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green’s function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approachmore » naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. Themethod is illustrated for the XPS and XAS of NH3.« less

Authors:
 [1];  [1];  [1];  [2];  [2]
+ Show Author Affiliations
  1. Univ. of Washington, Seattle, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1829677
Report Number(s):
PNNL-SA-163615
Journal ID: ISSN 2296-2646
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Frontiers in Chemistry
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2296-2646
Publisher:
Frontiers Research Foundation
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; coupled cluster; electronic structure; electronic structure calculations; Ab initio calculation; excited electronic states; computational chemistry

Citation Formats

Vila, Fernando D., Kas, Joshua J., Rehr, John J., Kowalski, Karol, and Peng, Bo. Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra. United States: N. p., 2021. Web. doi:10.3389/fchem.2021.734945.
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Vila, Fernando D., Kas, Joshua J., Rehr, John J., Kowalski, Karol, & Peng, Bo. Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra. United States. https://doi.org/10.3389/fchem.2021.734945
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Vila, Fernando D., Kas, Joshua J., Rehr, John J., Kowalski, Karol, and Peng, Bo. Wed . "Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra". United States. https://doi.org/10.3389/fchem.2021.734945. https://www.osti.gov/servlets/purl/1829677.
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@article{osti_1829677,
title = {Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra},
author = {Vila, Fernando D. and Kas, Joshua J. and Rehr, John J. and Kowalski, Karol and Peng, Bo},
abstractNote = {Green’s function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green’s function approach has been introduced, where the cumulant is obtained as the solution to a set of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green’s function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function associated with the core Green’s function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then obtained as a convolution of the core spectral function and an effective one-body absorption spectrum. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green’s function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approach naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. Themethod is illustrated for the XPS and XAS of NH3.},
doi = {10.3389/fchem.2021.734945},
journal = {Frontiers in Chemistry},
number = ,
volume = 9,
place = {United States},
year = {Wed Sep 22 00:00:00 EDT 2021},
month = {Wed Sep 22 00:00:00 EDT 2021}
}
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https://doi.org/10.3389/fchem.2021.734945
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