Coincidence ion pair production (I + + I − ) (cipp) spectra of I 2 were recorded in a double imaging coincidence experiment in the one-photon excitation region of 71 600–74 000 cm −1 . The I + + I − coincidence signal shows vibrational band head structure corresponding to iodine molecule Rydberg states crossing over to ion-pair (I + I − ) potential curves above the dissociation limit. The band origin ( ν 0 ), vibrational wavenumber ( ω e ) and anharmonicity constants ( ω e x e ) were determined for the identified Rydberg states. The analysis revealed a number of previously unidentified states and a reassignment of others following a discrepancy in previous assignments. Since the ion pair production threshold is well established, the electric field-dependent spectral intensities were used to derive the cutoff energy in the transitions to the rotational levels of the 7pσ(1/2) ( v ′ = 3) state.
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Resolving the F 2 bond energy discrepancy using coincidence ion pair production (cipp) spectroscopy
Coincidence ion pair production (cipp) spectra of F 2 were recorded on the DELICIOUS III coincidence spectrometer in the one-photon excitation region of 125 975–126 210 cm −1 . The F + + F − signal shows a rotational band head structure, corresponding to F 2 Rydberg states crossing over to the ion pair production surface. Spectral simulation and quantum defect analysis allowed the characterization of five new molecular Rydberg states (F 2 **): one Π and four Σ states. The lowest-energy Rydberg state spectrum observed ( T 0 = 125 999 cm −1 ) lacked some of the predicted rotational structure, which allowed an accurate determination of the ion pair production threshold of 15.6229 4 ± 0.0004 3 eV. Using the well-known atomic fluorine ionization energy and electron affinity, this number leads to a ground state F–F dissociation energy of 1.6012 9 ± 0.0004 4 eV. Photoelectron photoion coincidence (PEPICO) experiments were also carried out on F 2 and the dissociative photoionization threshold to F + + F was determined as 19.0242 ± 0.0006 eV. Using the atomic fluorine ionization energy, this can be converted to an F 2 dissociation energy of 1.6013 2 ± 0.0006 2 eV, further confirming the cipp-derived value above. Because the two experiments were independently energy-calibrated, they can be averaged to 1.6013 0 ± 0.0003 6 eV and this value can be used to derive the fluorine atom's 0 K heat of formation as 77.25 1 ± 0.01 7 kJ mol −1 . This latter is in excellent agreement with the latest Active Thermochemical Table (ATcT) value but improves its accuracy by almost a factor of three.
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- Award ID(s):
- 1665464
- NSF-PAR ID:
- 10282912
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 23
- Issue:
- 14
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 8292 to 8299
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1CP00140J
