Dyson orbitals within the fc-CVS-EOM-CCSD framework: theory and application to X-ray photoelectron spectroscopy of ground and excited states

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<br><div>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.</div>

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Dyson Orbitals within the fc-CVS-EOM-CCSD Framework: Theory and Application to X-ray Photoelectron Spectroscopy of Ground and Excited States

10.26434/chemrxiv.9616991.v2 ◽

2019 ◽

Cited By ~ 1

Author(s):

Marta L. Vidal ◽

Anna Krylov ◽

Sonia Coriani

Keyword(s):

Excited States ◽

Ground State ◽

Photoelectron Spectroscopy ◽

Equation Of Motion ◽

Photoelectron Spectra ◽

Coupled Cluster ◽

Time Resolved ◽

X Ray ◽

Target States

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<br><div>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.</div>

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Energy-Specific Equation-of-Motion Coupled-Cluster Methods for High-Energy Excited States: Application to K-edge X-ray Absorption Spectroscopy

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.5b00459 ◽

2015 ◽

Vol 11 (9) ◽

pp. 4146-4153 ◽

Cited By ~ 61

Author(s):

Bo Peng ◽

Patrick J. Lestrange ◽

Joshua J. Goings ◽

Marco Caricato ◽

Xiaosong Li

Keyword(s):

Excited States ◽

Absorption Spectroscopy ◽

High Energy ◽

Equation Of Motion ◽

Coupled Cluster ◽

X Ray ◽

Coupled Cluster Methods ◽

Specific Equation ◽

Cluster Methods ◽

X Ray Absorption

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Dyson Orbitals within the fc-CVS-EOM-CCSD Framework

10.26434/chemrxiv.9616991.v1 ◽

2019 ◽

Author(s):

Marta L. Vidal ◽

Anna Krylov ◽

Sonia Coriani

Keyword(s):

Excited States ◽

Cross Sections ◽

Ground State ◽

Equation Of Motion ◽

Photoelectron Spectra ◽

Coupled Cluster ◽

Time Resolved ◽

X Ray ◽

Ccsd Method

We report on the implementation and illustrative applications of Dyson orbitals within the recently proposed frozen-core (fc) core-valence separated (CVS) equation-of-motion (EOM) coupled-cluster singles and doubles (CCSD) method, which enables efficient and accurate characterization of core-ionized states. Dyson orbitals are reduced quantities that can be interpreted as correlated states of the ejected/attached electron.<br>Dyson orbitals enter the expressions of various experimental observables, such as photoionization cross sections; thus, they are necessary for modeling photoelectron spectra.<br>Here we discuss the simulations of X-ray photoelectron spectra (XPS) and propose an approach to simulate time-resolved (TR-)XPS for probing excited states. <br>As illustrative examples, we present the simulation of the XPS of the ground state of adenine and of TR-XPS of the excited states of uracil.

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