berkowitz_2008#
J. Berkowitz, “Absolute partial photoionization cross sections of ozone”, Int. J. Mass Spectrom. 271, 8 (2008)
Source record · Catalogue · Review register
DOI: 10.1016/j.ijms.2007.11.005
Source kind: compilation
Recorded technique: Evaluation, no new measurement: the partial photoionization cross sections of O3’s valence orbitals are those calculated by Padial et al. (1981, Stieltjes-Tchebycheff, static exchange; Fig. 2, reproduced); the absolute total photoionization cross section is Cook’s (1970) figure raised by about 40 % to Cook’s 1968 calibration, joined above 20.5 eV to Ogawa and Cook’s photoabsorption and Celotta et al.’s electron energy-loss intensities (Fig. 3); the partial cross sections of O3+, O2+ and O+ are Mocellin et al.’s relative ion yields turned into branching ratios on that total (Figs. 4, 5) (pp. 10-13).
Materials in structured entries: O3
Dataset quantities: absorption_cross_section
Contents: 2 datasets; 0 formulas.
Curation notes#
Journal pages 8-14 = PDF pages 1-7. Identity checked against the first page (title, author, Int. J. Mass Spectrom. 271 (2008) 8-14). Ozone only.
NO TABULATED CROSS SECTION: every total and partial cross section is in Figs. 2-5 only (not digitised). Table 1 (p. 10, image checked) is a CI interpretation of the valence photoelectron spectrum (Fig. 1, Wiesner et al. at 100 eV): relative band areas 2.05 (bands 1+2), 1.00 (3), 0.015 (4), 0.083 (5), 0.474 (6), 0.912 (8), 0.018 (10), 0.05 (11), with Ohtsuka et al.’s major configurations; not a cross section, not extracted.
COOK’S CALIBRATION, 1968 AGAINST 1970 (p. 11, quoted): ‘Cook [22,23] used a 50 cm absorption cell with parallel plates extending the length of the cell to make absolute photoionization (and photoabsorption) cross section measurements. The spectra he presented in 1970 indicated that the quantum yield of ionization is approaching unity at 600 A = 20.66 eV but his absolute scale of cross sections [23] had been reduced from his original calibration [22]. Using his 1968 calibration, which is preferred by sum rule analysis [24], leads to an enhancement in cross section by a factor 1.4 which has been used in constructing Fig. 3.’ And p. 12: ‘the available abstract [of 22] mentions little about ozone other than a maximum in the photoabsorption cross section of 42 Mb at 725 A. That datum is about 40% higher than shown in the 1970 figure, as previously noted ... As a working hypothesis, we have used Cook’s 1970 curve, increased by ~40%, as the absolute total photoionization cross section of ozone.’ [22] = G. R. Cook, Trans. Am. Geophys. Union 49 (1968) 736A; [23] = G. R. Cook, in Recent Developments in Mass Spectrometry, eds. K. Ogata and T. Hayakawa (University Park Press, Baltimore, 1970), p. 761; [24] = Berkowitz’s book (Atomic and Molecular Photoabsorption. Absolute Total Cross Sections, Academic Press, London, 2002), p. 228. Above 20.5 eV Celotta et al.’s EELS intensities were normalised to ‘Cook (revised)’ at 20.5 eV and to Ogawa and Cook (ogawa_1958) from 20.5 to 23.5 eV, and scaled by E^2 up to 30.3 eV; photoabsorption and photoionization are taken as equal above 21 eV (pp. 11-12). BEARING: kumar_2011 (supplement j = 18, 12.00-20.60 eV) takes this interval from Cook 1970 and rescales it by its constraints (1 + a = 1.34 for B1, 1.18 for C, 0.986 for A): B1 is close to Berkowitz’s 1.4, C in between. sakamoto_2010’s O3 continuum 11.24-20.66 eV is the book’s Fig. 5.12, i.e. Berkowitz’s evaluation (whether with the 1.4 is not stated there): to compare (TC-220).
IONISATION AND APPEARANCE ENERGIES of O3 (text; quoted with their sources, reproduced values, not datasets: the format has no quantity for them): adiabatic IP(X 2A1) = 12.52495(6) eV (Willitsch et al. 2005, PFI-ZEKE; p. 9, repeated p. 11), ‘in satisfactory agreement with’ 12.519(4) eV (Weiss et al. 1977, photoionization mass spectrometry), discounting a hot band at 12.44 eV; vertical IP = the (0 3 0) level of X 2A1, 12.7500 eV; A 2B2 (0 0 0) at 12.66004(7) eV; X 2A1 (0 2 0) at 12.6762 eV; most other work places the A-state vertical value at 13.00 eV (p. 9). Koopmans’ order 2A2 (13.43 eV) < 2A1 (15.28) < 2B2 (15.77) (Dyke et al.), reversed by CI (p. 9). Photoelectron peaks (p. 10): 3 at 13.54 eV; 4 at 15.6 eV (15.4, Wiesner et al.); 5 AIP 15.95, VIP 16.09 eV; 6 VIP 17.60 eV; 7 (shoulder) 19.4 eV; 8 VIP 20.1 eV; 9 VIP 20.9 eV; inner valence (4a1)^-1 at 26.8 eV; Koopmans values 29.86 (4a1), 39.58 (2b2), 48.55 eV (3a1) (Padial et al.). Appearance potentials (p. 12): O2+(O3) 13.1322(4) eV (from D0(O3 -> O(3P2) + O2) = 24.49(1) kcal/mol = 1.0621(4) eV, Taniguchi et al., and IP(O2) = 12.07014(15) eV, Merkt et al.); O+(O3) 14.6802(4) eV (IP(O) = 13.618055(7) eV, Moore); 2O + O+ 19.7668(2) eV; O3^2+ -> O2+ + O+ observed at about 34.3 eV (asymptotes 26.75 eV triplet, 30.07 eV singlet). Weiss et al.’s measured AP O2+(O3) 13.125(4) eV (0 K) and O+ onset 15.21(1) eV (p. 12). Numbers checked in the pdf text layer.
EXTRACTED: the two cross sections the text states (inline points, ‘check’ or ‘reproduced’). The Hartley-band maximum is quoted without a source, temperature or wavelength medium.
Recorded bibliographic identity status: VALIDATED. This concerns identification of the source; it does not establish the scientific correctness of its contents.
Datasets#
berkowitz_2008/hartley_maximum#
{
"id": "hartley_maximum",
"material": "O3",
"table": "text",
"quantity": "absorption_cross_section",
"unit": "Mb",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "check"
}
1 inline points in the source record.
p. 8: the Hartley band ‘has a high cross section between 2100 and 3000 A with a maximum of 11.73 Mb at 2555 A (4.85 eV)’. No source, temperature or medium stated; vacuum is assumed (hc/4.85 eV = 2556 A; the air/vacuum difference, 0.8 A, is below the precision of a band maximum). A quoted value with no source cited: ‘check’.
berkowitz_2008/cook_1968_maximum#
{
"id": "cook_1968_maximum",
"material": "O3",
"table": "text",
"quantity": "absorption_cross_section",
"unit": "Mb",
"abscissa_unit": "angstrom",
"wavelength_medium": "vacuum",
"use": "reproduced",
"reproduced_from": [
"G. R. Cook, Trans. Am. Geophys. Union 49 (1968) 736A"
]
}
1 inline points in the source record.
p. 12: Cook’s 1968 abstract gives ‘a maximum in the photoabsorption cross section of 42 Mb at 725 A’, ‘about 40% higher than shown in the 1970 figure’. Vacuum ultraviolet (725 A, 17.1 eV): vacuum wavelength. Temperature not stated.
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.