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Origin of alkylphosphonic acids in the interstellar medium

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Science Advances  07 Aug 2019:
Vol. 5, no. 8, eaaw4307
DOI: 10.1126/sciadv.aaw4307
  • Fig. 1 Adiabatic ionization energies (IE) and relative energies (ΔE) for methylphosphonic acid along with structural isomers calculated at the B3LYP/cc-pVTZ//CCSD(T)/CBS level of theory (CCSD(T)/CBS energy on B3LYP/cc-pVTZ optimized geometry).

  • Fig. 2 TPD profiles and integrated mass spectra at 9.93 and 10.49 eV depicting isotopically labeled PH3/H2O/CH4.

    PI-ReTOF-MS data recorded at photon energies of 9.93 eV (top row) and 10.49 eV (second row) as a function of temperature of the newly formed products subliming into the gas phase from the irradiated PH3/H2O/CH4 (left), PH3/H218O/CH4 (center), and PH3/H2O/13CH4 (right) ices. The integrated mass spectra at 9.93 eV (third row) and 10.49 eV (bottom row) are also shown, with the PH3/H2O/CH4 mixture shown in red, PH3/H218O/CH4 in green, and PH3/H2O/13CH4 in blue.

  • Fig. 3

    TPD profiles of photoionized H5CPO3 isomers along with their 18O and 13C substituted counterparts (H5CP18O3 and H513CPO3) recorded at m/z = 96, 102, and 97 subliming from the processed PH3 + H2O + CH4 (top), PH3 + H218O + CH4 (center), and PH3 + H2O + 13CH4 (bottom) ices. The TPD profiles are shown for photon energies of 9.93 eV (black), 10.35 eV (blue), and 10.49 eV (red). The middle right graph shows m/z = 98 for the PH3 + H218O + CH4 systems to demonstrate the presence of the H6CP2O compounds, which would also be present in the m/z = 96 (PH3 + H2O + CH4) and m/z = 97 (PH3 + H2O + 13CH4) signals.

  • Fig. 4 Organophosphorus compounds detected in the room temperature residues irradiated ices by multidimensional gas chromatography.

    The residues from PH3/H218O/CH4 (left) and PH3/H2O/13CH4 (right) ices are shown. Further details and scaled chromatograms are provided in the Supplementary Materials (figs. S3 and S4). In Murchison, 1 g of the meteorite contained 9 nmol of methylphosphonic acid and 6 nmol of ethylphosphonic acids.

Supplementary Materials

  • Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/5/8/eaaw4307/DC1

    Supplementary Text

    Table S1. Infrared absorption peaks before and after irradiation for PH3 + H2O/H218O + CH4/13CH4.

    Table S2. PI-ReTOF-MS ion counts detected from irradiation of the PH3 + H2O + CH4 ice mixture and confirmed using H218O and 13CH4.

    Table S3. Identified alkylphosphonic acids and phosphorus oxoacids as trimethylsilyl derivatives by GC×GC-TOF-MS.

    Table S4. Quantities of identified alkylphosphonic acids and phosphorus oxoacids in the PH3/H2O/13CH4 ice mixture and the irradiation yield (molecules eV−1).

    Fig. S1. Temperature programmed desorption profiles associated with mass-to-charge ratios (m/z) of H5CPO, H5CPO2, H5CPO3, and H5CPO4.

    Fig. S2. Calculated ionization energies (IE) and relative isomeric energies (ΔE) for the isomers of H5CPO, H5CPO2, H5CPO3, and H5CPO4.

    Fig. S3. Organophosphorus compounds detected in the room temperature residues irradiated ices composed of PH3/H218O/CH4 by multidimensional gas chromatography.

    Fig. S4. Organophosphorus compounds detected in the room temperature residues irradiated ices composed of PH3/H2O/13CH4 by multidimensional gas chromatography.

    Fig. S5. Time-of-flight mass spectra of silylated phosphorus compounds identified in the residue from irradiated ices of PH3/H2O/13CH4.

    Fig. S6. Time-of-flight mass spectra of silylated phosphorus compounds in the residue from irradiated ices of PH3/H218O/CH4.

    Fig. S7. Time-of-flight mass spectra of silylated methylphosphonic acid identified in residues of ices PH3/H218O/CH4 and PH3/H2O/13CH4.

    References (3743)

  • Supplementary Materials

    This PDF file includes:

    • Supplementary Text
    • Table S1. Infrared absorption peaks before and after irradiation for PH3 + H2O/H218O + CH4/13CH4.
    • Table S2. PI-ReTOF-MS ion counts detected from irradiation of the PH3 + H2O + CH4 ice mixture and confirmed using H218O and 13CH4.
    • Table S3. Identified alkylphosphonic acids and phosphorus oxoacids as trimethylsilyl derivatives by GC×GC-TOF-MS.
    • Table S4. Quantities of identified alkylphosphonic acids and phosphorus oxoacids in the PH3/H2O/13CH4 ice mixture and the irradiation yield (molecules eV−1).
    • Fig. S1. Temperature programmed desorption profiles associated with mass-to-charge ratios (m/z) of H5CPO, H5CPO2, H5CPO3, and H5CPO4.
    • Fig. S2. Calculated ionization energies (IE) and relative isomeric energies (ΔE) for the isomers of H5CPO, H5CPO2, H5CPO3, and H5CPO4.
    • Fig. S3. Organophosphorus compounds detected in the room temperature residues irradiated ices composed of PH3/H218O/CH4 by multidimensional gas chromatography.
    • Fig. S4. Organophosphorus compounds detected in the room temperature residues irradiated ices composed of PH3/H2O/13CH4 by multidimensional gas chromatography.
    • Fig. S5. Time-of-flight mass spectra of silylated phosphorus compounds identified in the residue from irradiated ices of PH3/H2O/13CH4.
    • Fig. S6. Time-of-flight mass spectra of silylated phosphorus compounds in the residue from irradiated ices of PH3/H218O/CH4.
    • Fig. S7. Time-of-flight mass spectra of silylated methylphosphonic acid identified in residues of ices PH3/H218O/CH4 and PH3/H2O/13CH4.
    • References (3743)

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