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Studies on photodissociation dynamics of butadiene monoxide at
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10.1063/1.2819105
/content/aip/journal/jcp/128/2/10.1063/1.2819105
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/2/10.1063/1.2819105

Figures

Image of FIG. 1.
FIG. 1.

LIF excitation spectrum of the (0,0) band of the system of the nascent OH radical formed in photodissociation of BMO at . Delay between pump and probe laser was . The rotational lines are marked in the figure.

Image of FIG. 2.
FIG. 2.

A Boltzmann plot of rotational state population against energy of rotational states of OH generated in dissociation of BMO with laser. From the slope of this plot, the rotational temperature of OH was estimated to be , which corresponds to of the rotational energy of the OH fragment.

Image of FIG. 3.
FIG. 3.

Doppler broadened line of the (0,0) system of the OH radical produced in dissociation of BMO with laser. Deconvolution of the peak profiles gives the average width of , corresponding to translational energy of .

Image of FIG. 4.
FIG. 4.

Distribution of ratio of spin-orbit state populations against rotational quantum number for the OH radical, produced in photodissociation of BMO with laser. Both spin-orbit levels are equally populated.

Image of FIG. 5.
FIG. 5.

Dependence of ratio of doublet populations on rotational quantum number for the nascent OH formed in laser-induced photodissociation of BMO at . Both doublet levels are statistically populated.

Image of FIG. 6.
FIG. 6.

A plot of vs the number density of BMO, results in the value of its absorption cross section to be .

Image of FIG. 7.
FIG. 7.

The plot shows formation of OH in different rotational levels (, 5, and 7), based on measurement of time evolution of the (0,0) band of lines. The figure shows faster formation of OH with increased .

Image of FIG. 8.
FIG. 8.

The optimized structures of the transition states and other products for two reaction pathways of the ring opening and subsequent generation of OH from the ground electronic state of BMO at the B3LYP level of theory using basis sets. Channels (1) and (2) lead to formation of enols of vinylacetaldehyde, Enol (1), and methyl vinyl ketone, Enol (2), which subsequently generate their keto tautomers, Keto (1) and Keto (2), in addition to OH. Crotonaldehyde, Keto (3), can be produced from Enol (1) or Birad (1) via TS4 (1) or TS5 (1), respectively. The breaking bonds are shown as dotted lines; some important distances (in angstrom) are marked.

Image of FIG. 9.
FIG. 9.

Potential energy diagram for formation of OH from the ground electronic state of BMO on excitation at involving enols of vinylacetaldehyde (dotted curves) and methyl vinyl ketone (solid curves). In addition, energetics of enol-keto tautomerization, with TS marked as TS3, are shown. Transition states for vinylacetaldehyde and methyl vinyl ketone from their respective biradicals are depicted as TS (6). TS4 (1) and TS5 (1) represent the TS for formation of crotonaldehyde, Keto (3), (dashed curves) from enol of vinylacetaldehyde, Enol (1), and Birad (1), respectively. Energies are calculated at the level, except those mentioned in parentheses are at level, after optimization of geometries at the level of theory. All energies are in .

Tables

Generic image for table
Table I.

Energies (in ) of various products including transition states at different levels of theory with basis sets , relative to the reactant BMO, and geometries optimized at level.

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/content/aip/journal/jcp/128/2/10.1063/1.2819105
2008-01-14
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Studies on photodissociation dynamics of butadiene monoxide at 193nm
http://aip.metastore.ingenta.com/content/aip/journal/jcp/128/2/10.1063/1.2819105
10.1063/1.2819105
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