Valence and inner-valence shell dissociative photoionization of CO in the 26–33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions

Lebech, M.; Houver, J. C.; Raşeev, G.; Santos, A. S.; Dowek, D.; Lucchese, Robert R.

doi:10.1063/1.3681920

Cited by 18 publications

(13 citation statements)

References 82 publications

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“…A notable difference with our results is the absence of Feshbach resonances in all previously reported calculations, except for a few resonances predicted by the MCSCI method. 47 At higher energies, the XCHEM results are compatible with those of other calculations. These results support the notion that our description of the nonresonant part of the electronic continuum is reliable also in the region where Feshbach resonances appear.…”

Section: Resultssupporting

confidence: 83%

Molecular-Frame Photoelectron Angular Distributions of CO in the Vicinity of Feshbach Resonances: An XCHEM Approach

Borràs

González‐Vázquez

Argenti

et al. 2021

J. Chem. Theory Comput.

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The advent of ultrashort XUV pulses is pushing for the development of accurate theoretical calculations to describe ionization of molecules in regions where electron correlation plays a significant role. Here, we present an extension of the XCHEM methodology to evaluate laboratory- and molecular-frame photoelectron angular distributions in the region where Feshbach resonances are expected to appear. The performance of the method is demonstrated in the CO molecule, for which information on Feshbach resonances is very scarce. We show that photoelectron angular distributions are dramatically affected by the presence of resonances, to the point that they can completely reverse the preferred electron emission direction observed in direct nonresonant photoionization. This is the consequence of significant changes in the electronic structure of the molecule when resonances decay, an effect that is mostly driven by electron correlation in the ionization continuum. The present methodology can thus be helpful for the interpretation of angularly resolved photoionization time delays in this and more complex molecules.

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Section: Resultssupporting

confidence: 83%

Molecular-Frame Photoelectron Angular Distributions of CO in the Vicinity of Feshbach Resonances: An XCHEM Approach

Borràs

González‐Vázquez

Argenti

et al. 2021

J. Chem. Theory Comput.

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“…The main configurations of this satellite peak include 5σ −2 1π * (∼64%), 4σ −1 5σ −1 1π * (∼21%), and 5σ −2 2π * (∼6%), which are consistent with MCS-CI and SAC-CI results. [91,92] Compared to the early Green's function/CI studies of the inner-valence ionization of N 2 and CO molecules [91,92,96,100,101], the GFCC-i(2,3) calculation exhibits better agreement than the GFCCSD calculation in terms of overall spectral function profile (that is, the consistent prediction of the significant satellite peaks). Note that the previous Green's function study [96] is able to provide more detailed information of the inner valence ionization by providing the positions of weaker satellite peaks which might not be observable in our present GFCC calculations.…”

Section: Resultsmentioning

confidence: 92%

Green’s function coupled cluster formulations utilizing extended inner excitations

Kowalski

2018

The Journal of Chemical Physics

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In this paper we analyze new approximations of the Green's function coupled cluster (GFCC) method where locations of poles are improved by extending the excitation level of inner auxiliary operators. These new GFCC approximations can be categorized as GFCC-i(n, m) method, where the excitation level of the inner auxiliary operators (m) used to describe the ionization potentials and electron affinities effects in the N −1 and N +1 particle spaces is higher than the excitation level (n) used to correlate the ground-state coupled cluster wave function for the N -electron system. Furthermore, we reveal the so-called "n+1" rule in this category (or the GFCC-i(n,n+1) method), which states that in order to maintain size-extensivity of the Green's function matrix elements, the excitation level of inner auxiliary operators Xp(ω) and Yq(ω) cannot exceed n+1. We also discuss the role of the moments of coupled cluster equations that in a natural way assures these properties. Our implementation in the present study is focused on the first approximation in this GFCC category, i.e. the GFCC-i(2,3) method. As our first practice, we use the GFCC-i(2,3) method to compute the spectral functions for the N2 and CO molecules in the inner and outer valence regimes. In comparison with the GFCCSD results, the computed spectral functions from the GFCC-i(2,3) method exhibit better agreement with the experimental results and other theoretical results, particularly in terms of providing higher resolution of satellite peaks and more accurate relative positions of these satellite peaks with respect to the main peak positions. arXiv:1809.06884v3 [cond-mat.str-el]

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“…The most detailed information is ideally embodied in the molecular frame angular distributions (MFPADS) that probe in great detail the dynamic of the ionization. A comprehensive investigation has been conducted only in CO [11]. A recent study of the H 2 molecule has shown the potential to image correlation contributions to the ground state wavefunction [12].…”

Section: Introductionmentioning

confidence: 99%

Photoionization Observables from Multi-Reference Dyson Orbitals Coupled to B-Spline DFT and TD-DFT Continuum

et al. 2022

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We present a theoretical model to compute the accurate photoionization dynamical parameters (cross-sections, asymmetry parameters and orbital, or cross-section, ratios) from Dyson orbitals obtained with the multi-state complete active space perturbation theory to the second order (MS-CASPT2) method. Our new implementation of Dyson orbitals in OpenMolcas takes advantage of the full Abelian symmetry point group and has the corrected normalization. The Dyson orbitals are coupled to an accurate description of the electronic continuum obtained with a multicentric B-spline basis at the DFT and TD-DFT levels. Two prototype diatomic molecules, i.e., CS and SiS, have been chosen due to their smallness, which hides important correlation effects. These effects manifest themselves in the appearance of well-characterized isolated satellite bands in the middle of the valence region. The rich satellite structures make CS and SiS the perfect candidates for a computational study based on our highly accurate MS-CASPT2/B-spline TD-DFT protocol.

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Valence and inner-valence shell dissociative photoionization of CO in the 26–33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions

Cited by 18 publications

References 82 publications

Molecular-Frame Photoelectron Angular Distributions of CO in the Vicinity of Feshbach Resonances: An XCHEM Approach

Molecular-Frame Photoelectron Angular Distributions of CO in the Vicinity of Feshbach Resonances: An XCHEM Approach

Green’s function coupled cluster formulations utilizing extended inner excitations

Photoionization Observables from Multi-Reference Dyson Orbitals Coupled to B-Spline DFT and TD-DFT Continuum

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