Ionization Cross Sections of F2 and Cl2 by Electron Impact

The photodissociation of ozone has been studied at 193 nm using high resolution photofragment translational spectroscopy. The results show six distinct peaks in the time-of-flight spectra for the O2 product and its momentum-matched O atom counterpart. The translational energy distributions determined from the time-of-flight spectra reveal the production of a range of electronic states of the photofragments. The product electronic states were identified based on the translational energy distributions, with the aid of state-resolved imaging experiments by Houston and co-workers. The results reveal the production of a substantial yield of highly excited triplet states of O2, recently suggested to play an important role in the stratospheric ozone balance. In addition, peaks corresponding to O2(a 1Δg) and O2(b 1Σg+) were observed, the latter confirming a previous report [A. A. Turnipseed et al., J. Chem. Phys. 95, 3244 (1991)]. Evidence was seen for a small contribution from the triple dissociation O3→3O(3P), and insight into the dissociation dynamics for this process was inferred from the translational energy distributions. Branching fractions and angular distributions were measured for all channels. The latter were found in general to yield negative β parameters, in contrast to what is seen at longer wavelengths.

Section: Results and Analysismentioning

confidence: 99%

Photodissociation of ozone at 193 nm by high-resolution photofragment translational spectroscopy

Stranges

Yang

Chesko

et al. 1995

“…The electron bombardment ionization cross sections are estimated roughly from the empirical formula proposed by Center and Mandl, 23 with the sum of atomic polarizabilities calculated from those of Miller and Bederson. 24 This estimate is not expected to be better than ±20%.…”

Section: F Branching Ratio For C-cl Bond Fission and C-c Bond Fissionmentioning

confidence: 99%

Chloroacetone photodissociation at 193 nm and the subsequent dynamics of the CH3C(O)CH2 radical—an intermediate formed in the OH + allene reaction en route to CH3 + ketene

Alligood

FitzPatrick

Szpunar

et al. 2011

We use a combination of crossed laser-molecular beam experiments and velocity map imaging experiments to investigate the primary photofission channels of chloroacetone at 193 nm; we also probe the dissociation dynamics of the nascent CH(3)C(O)CH(2) radicals formed from C-Cl bond fission. In addition to the C-Cl bond fission primary photodissociation channel, the data evidence another photodissociation channel of the precursor, C-C bond fission to produce CH(3)CO and CH(2)Cl. The CH(3)C(O)CH(2) radical formed from C-Cl bond fission is one of the intermediates in the OH + allene reaction en route to CH(3) + ketene. The 193 nm photodissociation laser allows us to produce these CH(3)C(O)CH(2) radicals with enough internal energy to span the dissociation barrier leading to the CH(3) + ketene asymptote. Therefore, some of the vibrationally excited CH(3)C(O)CH(2) radicals undergo subsequent dissociation to CH(3) + ketene products; we are able to measure the velocities of these products using both the imaging and scattering apparatuses. The results rule out the presence of a significant contribution from a C-C bond photofission channel that produces CH(3) and COCH(2)Cl fragments. The CH(3)C(O)CH(2) radicals are formed with a considerable amount of energy partitioned into rotation; we use an impulsive model to explicitly characterize the internal energy distribution. The data are better fit by using the C-Cl bond fission transition state on the S(1) surface of chloroacetone as the geometry at which the impulsive force acts, not the Franck-Condon geometry. Our data suggest that, even under atmospheric conditions, the reaction of OH with allene could produce a small branching to CH(3) + ketene products, rather than solely producing inelastically stabilized adducts. This additional channel offers a different pathway for the OH-initiated oxidation of such unsaturated volatile organic compounds, those containing a C=C=C moiety, than is currently included in atmospheric models.

“…The electron bombardment cross sections are estimated roughly from the empirical formula proposed by Center and Mandl, 19 with the sum of atomic polarizabilities calculated from those of Miller and Bederson. 20 This estimate is not expected to be better than Ϯ20%.…”

Section: ͑2͒mentioning

confidence: 99%

Dissociation dynamics of the methylsulfonyl radical and its photolytic precursor CH3SO2Cl

Alligood

FitzPatrick

Glassman

et al. 2009

The dissociation dynamics of methylsulfonyl radicals generated from the photodissociation of CH(3)SO(2)Cl at 193 nm is investigated by measuring product velocities in a crossed laser-molecular beam scattering apparatus. The data evidence three primary photodissociation channels of the precursor: S-Cl fission to produce Cl atoms and ground electronic state CH(3)SO(2) radicals, S-Cl fission to produce Cl atoms and electronically excited CH(3)SO(2) radicals, and S-CH(3) fission. Some of the vibrationally excited CH(3)SO(2) radicals undergo subsequent dissociation to CH(3) + SO(2), as do all of the electronically excited radicals. The velocities of the SO(2) products show that the vibrationally excited ground state CH(3)SO(2) radicals dissociate via a loose transition state having a small exit barrier beyond the endoergicity. Hence, a statistical recoil kinetic energy distribution should and does fit the distribution of velocities imparted to these SO(2) products. The electronically excited CH(3)SO(2) radicals also dissociate to CH(3) + SO(2), but with a larger average release to relative kinetic energy. Interestingly, when using 200 eV electron bombardment detection, the ground electronic state CH(3)SO(2) radicals having too little internal energy to dissociate are not observed at the parent CH(3)SO(2)(+) ion, but only at the CH(3)(+) daughter ion. They are distinguished by virtue of the velocity imparted in the original photolytic step; the detected velocities of the stable radicals are consistent with the calculated barrier of 14.6 kcal/mol for the dissociation of CH(3)SO(2) to CH(3) + SO(2). We present CCSD(T) calculations of the adiabatic excitation energy to the lowest excited state of CH(3)SO(2) radicals, the 1 (2)A(") state, as well as the vertical energy from the equilibrium geometry of that excited state to the 2 (2)A(") state, to aid in the experimental assignment.