mahla_2025

S. Mahla and B. Mehnen, “Photoionization dynamics of O2 and O3 for atmospheric and astrophysical applications”, J. Chem. Phys. 163, 234312 (2025)

Source record · Catalogue · Review register

DOI: 10.1063/5.0307721

Source kind: theory

Recorded technique: Molecular R-matrix photoionisation (close coupling) of O2 and O3 at the fixed equilibrium geometries of the neutrals (R(OO) = 2.282 a0 for O2, 2.415 a0 for O3, from NIST’s CCCBDB), target ions from full-valence CAS-CI (O2: CAS of five, 1844 neutral and 3692 ion configuration state functions), R-matrix radius 10 a0: total and partial-channel photoionisation cross sections, asymmetry parameters and the vertical ionisation potentials of the ionic states.

Materials in structured entries: O2, O3

Dataset quantities: ionization_energy

Contents: 8 datasets; 0 formulas.

Curation notes

PDF pages 1-11 (pages cited are PDF pages). Authors checked on the first page.

EXTRACTED. Table I (p. 5), ‘Vertical ionization potentials of O2 and O3 (in eV)’: the R-matrix values (this work) for six states of O2+ (X 2Pi_g, a 4Pi_u, A 2Pi_u, b 4Sigma_g-, B 2Sigma_g-, 3 2Pi_u) and three of O3+ (2A1, 2B2, 2A2, the 6a1, 4b2 and 1a2 holes), and the experimental values the table quotes, one dataset per footnote (reproduced: a Baltzer et al. PES; b Tonkyn et al. PFI; c Edqvist et al. PES; d Katsumata et al., Wiesner et al., Couto et al. PES; e Brundle, Frost et al., Dyke et al. PES; f Willitsch et al. PFI-ZEKE; ‘12.75^{e,f}’ belongs to both). Kind: vertical, as the caption says for the whole table (the PFI values are flagged in their notes). The final state is each row’s label.

ACCURACY. No uncertainty is stated. The R-matrix energies differ from experiment by up to 1.3 eV (O2’s X state 10.993 against 12.307 and 12.070; O2’s b state 20.133 against 18.171) because ‘unshifted, or raw, theoretical term energies’ are used and ‘the calculated IP values reflect the small, state-dependent errors in the target description’, with the fixed-nuclei approximation neglecting relaxation (p. 5): check values only.

NOT EXTRACTED. The total and partial photoionisation cross sections of O2 (seven ionic states, Figs. 1-2, against Brion et al., Samson et al., Zammit et al., the Leiden database and PHIDRATES) and O3 (Figs. 3-4, CAS-4 and CAS-5 convergence) and the asymmetry parameters are figures only; no table prints them. The ordering of O3+’s first three states, 2A1 < 2B2 < 2A2 (11.846, 12.086, 14.066 eV), is discussed on p. 6.

Recorded bibliographic identity status: VALIDATED. This concerns identification of the source; it does not establish the scientific correctness of its contents.

Datasets

mahla_2025/rmatrix_O2

{
  "id": "rmatrix_O2",
  "material": "O2",
  "file": "O2/mahla_2025__rmatrix_O2.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "check",
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column R-matrix: ‘The present IP values correspond to the cross-section thresholds obtained for each final ionic state’, the ‘unshifted, or raw, theoretical term energies’ of the full-valence CAS-CI ion at the neutral’s fixed equilibrium geometry (p. 5); the state assignments are taken from experiment, ‘as the R-matrix method does not inherently assign them’. Rows labelled by the final ionic state. The method ‘is specialized to provide accurate cross-sections’, not energies (p. 5).

mahla_2025/rmatrix_O3

{
  "id": "rmatrix_O3",
  "material": "O3",
  "file": "O3/mahla_2025__rmatrix_O3.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "check",
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column R-matrix: ‘The present IP values correspond to the cross-section thresholds obtained for each final ionic state’, the ‘unshifted, or raw, theoretical term energies’ of the full-valence CAS-CI ion at the neutral’s fixed equilibrium geometry (p. 5); the state assignments are taken from experiment, ‘as the R-matrix method does not inherently assign them’. Rows labelled by the final ionic state. The method ‘is specialized to provide accurate cross-sections’, not energies (p. 5).

mahla_2025/expt_baltzer_O2

{
  "id": "expt_baltzer_O2",
  "material": "O2",
  "file": "O2/mahla_2025__expt_baltzer_O2.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "P. Baltzer, B. Wannberg, L. Karlsson, M. C. Gothe and M. Larsson, Phys. Rev. A 45, 4374 (1992)"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote a, ‘PES. Reference 74’; rows labelled by the final ionic state as the table assigns them.

mahla_2025/expt_tonkyn_O2

{
  "id": "expt_tonkyn_O2",
  "material": "O2",
  "file": "O2/mahla_2025__expt_tonkyn_O2.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "tonkyn_1989"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote b, ‘Pulsed-field-ionization (PFI). Reference 75’; rows labelled by the final ionic state as the table assigns them. The caption calls every value vertical; a pulsed-field-ionization measurement locates the threshold of the state’s lowest level, so this value is likely an adiabatic threshold rather than a band maximum (an inference: the paper does not say). The original (tonkyn_1989/ie_O2, curated separately) confirms it: 97348 +- 2 cm^-1 = 12.0696 eV, defined as the transition O2+ X 2Pi_g F1 (v = 0, J = 1/2) <- O2 X 3Sigma_g- F2 (v = 0, J = 1), an adiabatic, rotationally resolved threshold; 12.070 is its rounding.

mahla_2025/expt_edqvist_O2

{
  "id": "expt_edqvist_O2",
  "material": "O2",
  "file": "O2/mahla_2025__expt_edqvist_O2.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "O. Edqvist, E. Lindholm, L. E. Selin and L. Asbrink, Phys. Scr. 1, 25 (1970)"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote c, ‘PES. Reference 76’; rows labelled by the final ionic state as the table assigns them.

mahla_2025/expt_katsumata_O3

{
  "id": "expt_katsumata_O3",
  "material": "O3",
  "file": "O3/mahla_2025__expt_katsumata_O3.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "S. Katsumata, H. Shiromaru and T. Kimura, Bull. Chem. Soc. Jpn. 57, 1784 (1984)",
    "K. Wiesner, R. F. Fink, S. L. Sorensen, M. Andersson, R. Feifel, I. Hjelte, C. Miron, A. Naves de Brito, L. Rosenqvist, H. Wang et al., Chem. Phys. Lett. 375, 76 (2003)",
    "H. Couto, A. Mocellin, C. D. Moreira, M. P. Gomes, A. Naves de Brito and M. C. A. Lopes, J. Chem. Phys. 124, 204311 (2006)"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote d, ‘PES. References 35, 41, and 42’; rows labelled by the final ionic state as the table assigns them.

mahla_2025/expt_brundle_O3

{
  "id": "expt_brundle_O3",
  "material": "O3",
  "file": "O3/mahla_2025__expt_brundle_O3.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "C. R. Brundle, Chem. Phys. Lett. 26, 25 (1974)",
    "D. C. Frost, S. T. Lee and C. A. McDowell, Chem. Phys. Lett. 24, 149 (1974)",
    "J. M. Dyke, L. Golob, N. Jonathan, A. Morris and M. Okuda, J. Chem. Soc., Faraday Trans. 2 70, 1828 (1974)"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote e, ‘PES. References 28-30’; rows labelled by the final ionic state as the table assigns them.

mahla_2025/expt_willitsch_O3

{
  "id": "expt_willitsch_O3",
  "material": "O3",
  "file": "O3/mahla_2025__expt_willitsch_O3.csv",
  "table": "tbl_0127e8228e7c",
  "quantity": "ionization_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "reproduced",
  "reproduced_from": [
    "S. Willitsch, F. Innocenti, J. M. Dyke and F. Merkt, J. Chem. Phys. 122, 024311 (2005)"
  ],
  "parameters": {
    "kind": "vertical",
    "final_state": "the row label (the ionic state)"
  }
}

Table I (p. 5), column Experimental, footnote f, ‘Pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE). Reference 77’; rows labelled by the final ionic state as the table assigns them. The caption calls every value vertical; a pulsed-field-ionization measurement locates the threshold of the state’s lowest level, so this value is likely an adiabatic threshold rather than a band maximum (an inference: the paper does not say).

Formulas

No formulas are recorded.

Corrections

No dataset errata are recorded in this source record.

Formula corrections, where recorded, appear with their formulas above. Curation notes may also discuss corrections or unresolved interpretation. Consult the review register for the checks and decisions.