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B-Spline Solution of the Two-Center Dirac Equation in the Electronic Continuum for Relativistic Molecular Photoionization

Zapata, Felipe ; Toffoli, Daniele ; Dahlström, Jan Marcus LU ; Lindroth, Eva ; Decleva, Piero and Martín, Fernando (2024) In Journal of Chemical Theory and Computation 20(23). p.10507-10523
Abstract

In this work, the two-center Dirac equation is solved numerically using an extension of an adapted B-spline basis set method previously implemented in relativistic atomic calculations (Fischer, C. F.; Zatsarinny, O. Comput. Phys. Commun. 2009, 180, 879). The robustness of the chosen numerical method, which avoids the appearance of spurious states common in other approaches, allows us to investigate molecular photoionization within a relativistic framework by simply adapting those methods already available in the nonrelativistic case (Brosolo, M.; Decleva, P. Chem. Phys. 1992, 159, 185; Brosolo, M.; Decleva, P.; Lisini, A. Mol. Opt. Phys. 1992, 25, 3345). First, light diatomic molecules (i.e., H2+ and... (More)

In this work, the two-center Dirac equation is solved numerically using an extension of an adapted B-spline basis set method previously implemented in relativistic atomic calculations (Fischer, C. F.; Zatsarinny, O. Comput. Phys. Commun. 2009, 180, 879). The robustness of the chosen numerical method, which avoids the appearance of spurious states common in other approaches, allows us to investigate molecular photoionization within a relativistic framework by simply adapting those methods already available in the nonrelativistic case (Brosolo, M.; Decleva, P. Chem. Phys. 1992, 159, 185; Brosolo, M.; Decleva, P.; Lisini, A. Mol. Opt. Phys. 1992, 25, 3345). First, light diatomic molecules (i.e., H2+ and HeH2+) are investigated with the purpose of testing the validity and efficiency of the method. Then, a series of one-electron molecular hydrides (i.e., HF9+, HCl17+ and HI53+) is explored by computing the total photoionization cross sections, asymmetry β-parameters and partial phase shifts. The present methodology can be easily extended to treat N-electron molecules following previous approaches in nonrelativistic calculations (Plesiat, E.; Decleva, P.; Martin, F. Phys. Chem. Chem. Phys. 2012, 14, 10853). The inclusion of a second photon can be also accomplished just like in atomic investigations aiming at reproducing pump-probe experiments capable to extract the photoionization time-delays (Vinbladh, J.; Dahlstrom, J. M.; Lindroth, E. Phys. Rev A 2019, 100, 043424; Vinblach, J.; Dahlstrom, J. M.; Lindroth, E. Atoms 2022, 10, 80).

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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
20
issue
23
pages
17 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • pmid:39620370
  • scopus:85210921918
ISSN
1549-9618
DOI
10.1021/acs.jctc.4c01232
language
English
LU publication?
yes
id
1b1d4c36-e0d3-4123-b537-a59904b2aeb4
date added to LUP
2025-01-17 11:10:50
date last changed
2025-03-28 18:17:14
@article{1b1d4c36-e0d3-4123-b537-a59904b2aeb4,
  abstract     = {{<p>In this work, the two-center Dirac equation is solved numerically using an extension of an adapted B-spline basis set method previously implemented in relativistic atomic calculations (Fischer, C. F.; Zatsarinny, O. Comput. Phys. Commun. 2009, 180, 879). The robustness of the chosen numerical method, which avoids the appearance of spurious states common in other approaches, allows us to investigate molecular photoionization within a relativistic framework by simply adapting those methods already available in the nonrelativistic case (Brosolo, M.; Decleva, P. Chem. Phys. 1992, 159, 185; Brosolo, M.; Decleva, P.; Lisini, A. Mol. Opt. Phys. 1992, 25, 3345). First, light diatomic molecules (i.e., H<sub>2</sub><sup>+</sup> and HeH<sup>2+</sup>) are investigated with the purpose of testing the validity and efficiency of the method. Then, a series of one-electron molecular hydrides (i.e., HF<sup>9+</sup>, HCl<sup>17+</sup> and HI<sup>53+</sup>) is explored by computing the total photoionization cross sections, asymmetry β-parameters and partial phase shifts. The present methodology can be easily extended to treat N-electron molecules following previous approaches in nonrelativistic calculations (Plesiat, E.; Decleva, P.; Martin, F. Phys. Chem. Chem. Phys. 2012, 14, 10853). The inclusion of a second photon can be also accomplished just like in atomic investigations aiming at reproducing pump-probe experiments capable to extract the photoionization time-delays (Vinbladh, J.; Dahlstrom, J. M.; Lindroth, E. Phys. Rev A 2019, 100, 043424; Vinblach, J.; Dahlstrom, J. M.; Lindroth, E. Atoms 2022, 10, 80).</p>}},
  author       = {{Zapata, Felipe and Toffoli, Daniele and Dahlström, Jan Marcus and Lindroth, Eva and Decleva, Piero and Martín, Fernando}},
  issn         = {{1549-9618}},
  language     = {{eng}},
  number       = {{23}},
  pages        = {{10507--10523}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Journal of Chemical Theory and Computation}},
  title        = {{B-Spline Solution of the Two-Center Dirac Equation in the Electronic Continuum for Relativistic Molecular Photoionization}},
  url          = {{http://dx.doi.org/10.1021/acs.jctc.4c01232}},
  doi          = {{10.1021/acs.jctc.4c01232}},
  volume       = {{20}},
  year         = {{2024}},
}