Isotope-selective photodissociation of ozone molecules induced by infrared laser irradiation

Kuze, Hiroaki; Sato, Tetsuya; Kambe, T.; Hayashida, Shigeru; Tatsumi, Yasuo

doi:10.1016/j.cplett.2008.02.080

Cited by 3 publications

(2 citation statements)

References 11 publications

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“…Furthermore, literature studies have shown that excitation of the Chappuis and Wulf bands with λ ≤ 600 nm causes the photodissociation of O 3 , resulting in the formation of groundstate O( 3 P) and O 2 ( 3 Σ). 15,35 This is precisely the result obtained in the infrared studies, where red-light irradiation led to O atom reaction with the ferrocene in the complex and product formation. Comparable results were seen here.…”

Section: ■ Results and Discussionsupporting

confidence: 77%

Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV–vis Matrix-Isolation Study

2015

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The reactions of ozone with ferrocene (cp2Fe) and with n-butylferrocene (n-butyl cp2Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp2Fe with O3 and of n-butyl cp2Fe with O3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n→ π* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp2Fe or n-butyl cp2Fe affects how readily the π* orbital on O3 is populated when red light (λ ≥ 600 nm) is absorbed. 1:1 complexes of cp2Fe and n-butyl cp2Fe with O2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photooxidation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.

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Section: ■ Results and Discussionsupporting

confidence: 77%

Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV–vis Matrix-Isolation Study

2015

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“…A related study has shown that while ozone (with a mixture of different isotopologues) was irradiated with narrow linewidth laser, the isotopologue corresponding to that wavelength dissociated proportional to the laser linewidth. 32 The important point this conveys is that irradiating a gas with narrow linewidth is different from that irradiating with a broad beam. The former specifically excites the corresponding isotopologue, whereas the latter excites all the isotopologues in its wavelength range, and hence the complicated overlapping of the wave functions of the excited ro-vibrational states occurs, giving rise to large scale perturbations.…”

Section: Evaluation Of Isotopic Self-shielding In Nmentioning

confidence: 99%

Nitrogen isotopic fractionations in the low temperature (80 K) vacuum ultraviolet photodissociation of N2

Chakraborty

Jackson

Rude

et al. 2016

The Journal of Chemical Physics

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N2 is a diatomic molecule with complex electronic structure. Interstate crossings are prominent in the high energy domain, introducing significant perturbations to the system. Nitrogen mainly photodissociates in the vacuum ultraviolet (VUV) region of the electromagnetic spectrum through both direct and indirect predissociation. Due to the complexity introduced by these perturbations, the nitrogen isotopic fractionation in N2 photodissociation is extremely hard to calculate, and an experimental approach is required. Here we present new data of N-isotopic fractionation in N2 photodissociation at low temperature (80 K), which shows a distinctly different 15N enrichment profile compared to that at relatively higher temperatures (200 and 300 K). The new data, important to understanding the N-isotopic compositions measured in meteorites and other planetary bodies, are discussed in light of the knowledge of N2 photochemistry and calculated photoabsorption cross sections in the VUV.

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Isotope separation of 17O by photodissociation of ozone with near-infrared laser irradiation

Hayashida¹,

Kambe²,

Sato³

et al. 2012

Journal of Applied Physics

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Oxygen-17 is a stable oxygen isotope useful for various diagnostics in both engineering and medical applications. Enrichment of 17O, however, has been very costly due to the lack of appropriate methods that enable efficient production of 17O on an industrial level. In this paper, we report the first 17O-selective photodissociation of ozone at a relatively high pressure, which has been achieved by irradiating a gas mixture of 10 vol% O3-90 vol% CF4 with narrowband laser. The experiment was conducted on a pilot-plant scale. A total laser power of 1.6 W was generated by external-cavity diode lasers with all the laser wavelengths fixed at the peak of an absorption line of 16O16O17O around 1 μm. The beams were introduced into a 25 -m long photoreaction cell under the sealed-off condition with a total pressure of 20 kPa. Lower cell temperature reduced the background decomposition of ozone, and at the temperature of 158 K, an 17O enrichment factor of 2.2 was attained.

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Isotope-selective photodissociation of ozone molecules induced by infrared laser irradiation

Cited by 3 publications

References 11 publications

Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV–vis Matrix-Isolation Study

Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV–vis Matrix-Isolation Study

Nitrogen isotopic fractionations in the low temperature (80 K) vacuum ultraviolet photodissociation of N2

Isotope separation of 17O by photodissociation of ozone with near-infrared laser irradiation

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