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Br2 molecular elimination in photolysis of (COBr)2 at 248 nm by using cavity ring-down absorption spectroscopy: A photodissociation channel being ignored
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10.1063/1.3664782
/content/aip/journal/jcp/135/23/10.1063/1.3664782
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/23/10.1063/1.3664782

Figures

Image of FIG. 1.
FIG. 1.

A portion of Br2 spectra acquired in the photolysis of (COBr)2 at 248 nm. (a) Trace acquired experimentally for the band of v = 0 contained in the 515–518 nm region, (b) the simulated counterpart, (c) the spectrum of pure Br2 molecule, and (d) the background spectrum obtained without irradiation of 248 nm. Partial assignments are added.

Image of FIG. 2.
FIG. 2.

A portion of Br2 spectra acquired in the photolysis of (COBr)2 at 248 nm. (a) Trace acquired experimentally for the bands of v = 0 and 1contained in the 522–524 nm region, (b) the simulated counterpart with the population ratio of Br2 (v = 1)/Br2 (v = 0) optimized at 0.65, (c) simulated counterpart with the transition involving only v = 0, and (d) simulated counterpart with the transition involving only v = 1.

Image of FIG. 3.
FIG. 3.

A portion of Br2 spectra acquired in the photolysis of (COBr)2 at 248 nm. (a) Trace acquired experimentally for the bands of v = 0, 1, and 2 contained in the 534–535 nm region, (b) the simulated counterpart with the population ratio of Br2 (v = 1)/Br2 (v = 0) fixed at 0.65 and Br2 (v = 2)/Br2 (v = 0) adjusted to 0.34, (c) simulated counterpart with the transition involving only v = 0, (d) simulated counterpart with the transition involving only v = 1, and (e) simulated counterpart with the transition involving only v = 2.

Image of FIG. 4.
FIG. 4.

Laser energy dependence of Br2 fragment intensity at 519.68 nm contributed mainly from the rotational line P(37) of the (35,0) band.

Image of FIG. 5.
FIG. 5.

Br2 fragment intensity as a function of (COBr)2 pressure varied from 100 to 500 mTorr. The rotational line at 519.68 nm is selected for the measurements.

Image of FIG. 6.
FIG. 6.

(a) Comparison of the Br2 spectra acquired under the conditions (i) with and (ii) without addition of 50 mTorr n-hexane to 250 mTorr oxalyl bromide. (b) Comparison of the Br2 spectra acquired in (i) the absence of diethyl ether to 400 mTorr oxalyl bromide, and in the presence of (ii) 30 mTorr, (iii) 120 mTorr, (iv) 425 mTorr, and (v) 655 mTorr diethyl ether to 400 mTorr oxalyl bromide. (vi) Spectral simulation of pure Br2.

Image of FIG. 7.
FIG. 7.

The dissociation channel initiated from the ground state potential energy surface of (COBr)2 in trans form. The energies in units of kJ/mol are calculated by CCSD(T)/6-311+G(2df) with B3LYP/6-31+G(d) zero-point energy correction.

Image of FIG. 8.
FIG. 8.

The related structures along the dissociation pathway of (COBr)2.

Image of FIG. 9.
FIG. 9.

Temperature dependence of the line intensity of Br2 at 522.452 nm contributed mainly from the rotational line P(12) of the (31,0) band.

Tables

Generic image for table
Table I.

The calculated energies of the B3LYP/6-31+G(d) optimized geometries for the Br2 dissociation channels on the adiabatic singlet ground state potential energy surface of (COBr)2.

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/content/aip/journal/jcp/135/23/10.1063/1.3664782
2011-12-20
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Br2 molecular elimination in photolysis of (COBr)2 at 248 nm by using cavity ring-down absorption spectroscopy: A photodissociation channel being ignored
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/23/10.1063/1.3664782
10.1063/1.3664782
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