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Absorptions between 3000 and 5500 cm(-1) of cyclic O4+ and O4- trapped in solid neon
Marilyn E Jacox1, Warren E Thompson
1Sensor Science Division, National Institute of Standards and Technology , Gaithersburg, Maryland 20899-8441, United States.
The Journal of Physical Chemistry. A
|August 16, 2013
Summary
Neon matrix isolation spectroscopy confirmed gas-phase findings for cyclic ozone tetramer cation (cyc-O4+) and anion (cyc-O4-). Isotopic substitution aided in spectral assignments for these novel oxygen species.
Area of Science:
- Spectroscopy
- Inorganic Chemistry
- Quantum Chemistry
Background:
- Gas-phase studies have previously identified combination bands for ground-state cyclic ozone tetramer cation (cyc-O4+) in the 3000-4300 cm(-1) region.
- An electronic transition of the cyclic ozone tetramer anion (cyc-O4-) complexed with argon was observed in the gas phase between 4000 and 5300 cm(-1).
Purpose of the Study:
- To investigate the spectroscopic properties of cyclic ozone tetramer cation (cyc-O4+) and anion (cyc-O4-) in a low-temperature neon matrix environment.
- To compare neon matrix data with existing gas-phase experimental results for cyc-O4+ and cyc-O4-.
- To utilize isotopic substitution to aid in the assignment of observed spectral bands.
Main Methods:
- Neon matrix isolation spectroscopy at 4.3 K.
- Observation of infrared absorptions in the 3000-5300 cm(-1) spectral range.
- Comparison of experimental data with gas-phase results and theoretical calculations.
- Isotopic substitution experiments (e.g., using O-18) to confirm assignments.
Main Results:
- Spectroscopic absorptions corresponding to both cyc-O4+ and cyc-O4- were successfully observed in solid neon matrices.
- The observed matrix absorptions closely matched the spectral features reported in gas-phase experiments.
- Isotopic substitution provided crucial evidence supporting the proposed assignments for the vibrational and electronic transitions.
Conclusions:
- Neon matrix isolation spectroscopy is a viable technique for studying transient oxygen species like cyc-O4+ and cyc-O4-.
- The study validates and extends previous gas-phase assignments for these cyclic ozone tetramer ions.
- The findings contribute to a better understanding of the structure and spectroscopy of novel oxygen allotropes.
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