grebenshchikov_2007#

S. Yu. Grebenshchikov, Z.-W. Qu, H. Zhu and R. Schinke, “New theoretical investigations of the photodissociation of ozone in the Hartley, Huggins, Chappuis, and Wulf bands”, Phys. Chem. Chem. Phys. 9, 2044 (2007)

Source record · Catalogue · Review register

DOI: 10.1039/b701020f

Source kind: theory

Recorded technique: A review of the authors’ quantum-dynamics studies of the four absorption bands of O3 (200-1100 nm). Electronic structure: MRCI with single and double excitations from state-averaged full-valence CASSCF (18 electrons in 12 orbitals), Davidson correction, aug-cc-pVTZ for the global surfaces (cc-pVQZ for 1 3A’), MOLPRO; Table 1’s thresholds, geometries, vertical energies and band origins from new aug-cc-pVQZ calculations made for the review (pp. 2045-2047). Wave-packet dynamics on diabatic surfaces, surface hopping for the B/R crossing (pp. 2047-2049).

Materials in structured entries: O3

Dataset quantities: dissociation_energy, transition_dipole_moment

Contents: 11 datasets; 0 formulas.

Curation notes#

Identity checked on the first page (PDF page 1 = journal p. 2044): Grebenshchikov, Qu, Zhu and Schinke, Phys. Chem. Chem. Phys. 9, 2044-2064 (2007), a review (‘Invited Article’). PDF page n = journal page 2043 + n. O3 only.

PRODUCT CHANNELS (eqns (1)-(5), p. 2045): the photon energy above which each channel opens, ‘the corresponding experimental threshold energies’ (Table 1 footnote b), given without a reference: 1.051 eV O(3P) + O2(X 3Sigma_g-); 2.026 eV O(3P) + O2(a 1Delta_g); 2.678 eV O(3P) + O2(b 1Sigma_g+); 3.016 eV O(1D) + O2(X 3Sigma_g-); 3.999 eV O(1D) + O2(a 1Delta_g); and (p. 2062) 4.651 eV O(1D) + O2(b 1Sigma_g+). Inline datasets, use = check (their origin is not cited). Energies from O3(X~) in its ground vibrational state (Fig. 1 caption: ‘E = 0 corresponds to O3(X~) in the ground vibrational state’), so D0.

TABLE 1 (p. 2047; CSV, image checked, all cells agree): the calculated D0 of channels (1), (2) and (5) (1.01, 2.00, 3.95 eV), written; the transition dipole moments at the FC point, written. Not written (no quantity holds them as printed, or not asked): the equilibrium bond lengths and angles, the harmonic-like frequencies ‘extracted from the calculated absorption cross sections’ (with references c-j), the vertical energies T_v (1.561 1 3A’, 1.588 1 3A’’, 1.717 2 3A’’, 1.923 1 1A’’, 1.991 2 1A’’, 4.936 eV 3 1A’; with the X~ zero-point energy 0.176 eV ‘taken into account’), and the band origins T0 calculated (1.305, 1.483, 1.217, -, 2.086, 3.44 eV) and experimental (1.297, 1.455, 1.184, -, 2.059, 3.361 eV, from refs. 38, 20, 51, 20, 52). The X~ equilibrium energy at this level is -225.20357642 hartree.

QUANTUM YIELDS (notes only): in the Hartley band ‘the observed quantum yield of this channel [channel (5), O(1D) + O2(a 1Delta_g)] is as high as 85-90 %’ (p. 2049) and ‘About 10-15 % of the products reach the triplet channel (1)’ (p. 2050), both citing Houston’s review (ref. 13: P. L. Houston, in Modern Trends in Chemical Reaction Dynamics, Part 2, World Scientific, 2005). No wavelength is given and the values are ranges quoted from a review of other measurements: not taken (data rule 6). The spin-forbidden channels (2)-(4) are ‘very weakly populated’ and seen in the Huggins band (refs. 14-18, p. 2045).

Other figures of the paper, not taken: the calculated Hartley absorption ‘within 15 % of the experimental value’ at the maximum (p. 2048); the Chappuis calculation ‘overestimates the absolute value near the maximum by 25 %’ (p. 2057); the isolated Wulf band ‘only ~1.4 x 10^-22 cm^2 at the maximum’ (p. 2059); the Wulf (0,0,0) and 3B2 linewidths (p. 2061).

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

Datasets#

grebenshchikov_2007/d0_channel_1#

{
  "id": "d0_channel_1",
  "material": "O3",
  "file": "O3/grebenshchikov_2007__d0_channel_1.csv",
  "table": "tbl_6aebd02f5e84",
  "quantity": "dissociation_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "check",
  "parameters": {
    "kind": "D0",
    "products": "O(3P) + O2(X 3Sigma_g-)"
  }
}

Table 1 (p. 2047), row D0, the channel ‘3P/3Sigma (1)’ (columns 1 1A’ (X~), 1 3A’, 1 3A’’, 1 1A’’, all 1.01): the calculated threshold of channel (1), MRCI+Q/aug-cc-pVQZ. The row label is the eqn number. Against the experimental 1.051 eV of eqn (1) (exp_channel_1). Uncertainty not stated.

grebenshchikov_2007/d0_channel_2#

{
  "id": "d0_channel_2",
  "material": "O3",
  "file": "O3/grebenshchikov_2007__d0_channel_2.csv",
  "table": "tbl_6aebd02f5e84",
  "quantity": "dissociation_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "check",
  "parameters": {
    "kind": "D0",
    "products": "O(3P) + O2(a 1Delta_g)"
  }
}

Table 1 (p. 2047), row D0, the channel ‘3P/1Delta (2)’ (column 2 3A’’): 2.00 eV, calculated. Against the experimental 2.026 eV of eqn (2).

grebenshchikov_2007/d0_channel_5#

{
  "id": "d0_channel_5",
  "material": "O3",
  "file": "O3/grebenshchikov_2007__d0_channel_5.csv",
  "table": "tbl_6aebd02f5e84",
  "quantity": "dissociation_energy",
  "unit": "eV",
  "abscissa": "label",
  "use": "check",
  "parameters": {
    "kind": "D0",
    "products": "O(1D) + O2(a 1Delta_g)"
  }
}

Table 1 (p. 2047), row D0, the channel ‘1D/1Delta (5)’ (columns 2 1A’’, 3 1A’): 3.95 eV, calculated. Against the experimental 3.999 eV of eqn (5).