2015
DOI: 10.1039/c4cp06043a
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Characterization of molecular channel in photodissociation of SOCl2 at 248 nm: Cl2 probing by cavity ring-down absorption spectroscopy

Abstract: A primary elimination channel of the chlorine molecule in the one-photon dissociation of SOCl2 at 248 nm was investigated using cavity ring-down absorption spectroscopy (CRDS). By means of spectral simulation, the ratio of the vibrational population in the v = 0, 1, and 2 levels was evaluated to be 1 : (0.10 ± 0.02) : (0.009 ± 0.005), corresponding to a Boltzmann vibrational temperature of 340 ± 30 K. The Cl2 molecular channel was obtained with a quantum yield of 0.4 ± 0.2 from the X(1)A' ground state of SOCl2… Show more

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Cited by 9 publications
(18 citation statements)
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“…In order to verify whether the obtained transition states correspond to the desired process, internal reaction coordinate (IRC) calculations were carried out. On the basis of the obtained stationary points, more accurate energies were then obtained by single‐point calculations at the CCSD(T) level employing the correlation consistent triple ζ basis set cc‐pVTZ, which has been proved to achieve good agreement between computational and experimental results . Because of the lack of proper scaling factors for the level of theory used here, the CCSD(T) energies were corrected for the unscaled ω B97X‐D ZPVE.…”
Section: Theoretical Methodsmentioning
confidence: 99%
“…In order to verify whether the obtained transition states correspond to the desired process, internal reaction coordinate (IRC) calculations were carried out. On the basis of the obtained stationary points, more accurate energies were then obtained by single‐point calculations at the CCSD(T) level employing the correlation consistent triple ζ basis set cc‐pVTZ, which has been proved to achieve good agreement between computational and experimental results . Because of the lack of proper scaling factors for the level of theory used here, the CCSD(T) energies were corrected for the unscaled ω B97X‐D ZPVE.…”
Section: Theoretical Methodsmentioning
confidence: 99%
“…In comparison with this result, the quantum yields of Br 2 and I 2 produced from photodissociation of CH 2 Br 2 23,27 and CH 2 I 2 , 26 at the same wavelength yielded values of 0.21 ± 0.06 and 0.004 ± 0.0025, respectively. The quantum yield for the ICl channel from CH 2 ICl is smaller by a factor of 4 than that of Br 2 from CH 2 Br 2 but 10 times larger than that of I 2 from CH 2 I 2 .…”
Section: Resultsmentioning
confidence: 56%
“…Alternatively, the quantum yield for the ICl channel can be determined by the indirect method, when the quantum yields of similar reactions are well established. The Br 2 formation from CH 2 Br 2 photodissociation studied in previous work was chosen as a reference reaction with a quantum yield of 0.21 ± 0.06. , The following equation is used to calculate the quantum yield of ICl production where [ICl] and [Br 2 ] are concentrations obtained from the experiment, n CH 2 ICl and n CH 2 Br 2 are the number densities of CH 2 ICl and CH 2 Br 2 , and σ CH 2 ICl and σ CH 2 Br 2 are the absorption cross sections of CH 2 ICl and CH 2 Br 2 at 248 nm. We evaluated the Br 2 concentration to be 8.1 × 10 15 molecules/cm 3 at the rotational line of 519.68 nm by ring-down time measurements, and n CH 2 Br 2 was experimentally controlled to 596 mTorr.…”
Section: Resultsmentioning
confidence: 99%
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“…As demonstrated with cavity ring-down absorption spectroscopy (CRDS), we have successfully monitored the Br 2 and I 2 fragments eliminated from a series of halogen-containing hydrocarbons. We also observed a primary product of Br 2 in one-photon dissociation of (COBr) 2 at 248 nm and proposed a plausible reaction mechanism for the products Br 2 + 2CO .…”
Section: Introductionmentioning
confidence: 99%