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Photodissociation of vinyl cyanide at 193 nm: Nascent product distributions of the molecular elimination channels
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10.1063/1.3065986
/content/aip/journal/jcp/130/4/10.1063/1.3065986
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/4/10.1063/1.3065986

Figures

Image of FIG. 1.
FIG. 1.

Time-resolved IR emission spectra collected following the 193 nm photodissociation of vinyl cyanide.

Image of FIG. 2.
FIG. 2.

Time-resolved IR emission spectra collected following the 193 nm photodissociation of fully deuterated vinyl cyanide.

Image of FIG. 3.
FIG. 3.

Comparison of early time emission spectra following the 193 nm photodissociation of deuterated vinyl cyanide (…..) and deuterated vinyl bromide (____).

Image of FIG. 4.
FIG. 4.

Experimental (…..) spectrum collected after the dissociation of deuterated vinyl cyanide overlaid with the calculated best fit spectrum (____) of deuterated acetylene obtained using Eqs. (9) and (10).

Image of FIG. 5.
FIG. 5.

DCCD population distributions as a function of time following the 193 nm dissociation of deuterated vinyl cyanide.

Image of FIG. 6.
FIG. 6.

Measured variation of the average energy of the highly rovibrationally excited DCCD (collisionally quenched with 4 Torr He) as a function of time along with an overlaid exponential fit function. The zero-time point has been estimated through backextrapolation of the exponential fit.

Image of FIG. 7.
FIG. 7.

Experimental (…..) spectrum collected after the dissociation of vinyl cyanide overlaid with the calculated best fit spectrum (____) of hydrogen isocyanide obtained using Eqs. (9) and (10).

Image of FIG. 8.
FIG. 8.

Measured variation of the vibrational temperature of rovibrationally excited HNC (collisionally quenched with 4 Torr He) as a function of time along with an overlaid double exponential fit function. The zero-time point has been estimated through backextrapolation. The inset shows the corresponding average internal energy content of the HNC ensemble as a function of time.

Image of FIG. 9.
FIG. 9.

Measured branching ratio of highly rovibrationally excited DCCD (three-center elimination) relative to the total DCCD population. The initial four points represent results obtained from fitting two partially resolved DCCD features, highly excited DCCD as well minimally excited DCCD. Points 6–15 correspond to an unresolved mixture of the two features, and the final five points were obtained by assuming a single representative vibrational temperature.

Tables

Generic image for table
Table I.

The spectral assignment (fundamental transition frequencies and molecular nature) for the observed features in the time-resolved IR emission spectra following the 193 nm photodissociation of vinyl cyanide. Also listed are the photodissociation channels leading to the production of the observed species.

Generic image for table
Table II.

The spectral assignment (fundamental transition frequencies and molecular nature) for the observed features in the time-resolved IR emission spectra following the 193 nm photodissociation of vinyl cyanide-d3. Also listed are the photodissociation channels leading to the production of the observed species.

Generic image for table
Table III.

Experimental and calculated (statistical and impulsive analysis) energy distributions for the nascent products from the and reactions following 193 nm photodissociation of vinyl cyanide. Additionally, the associated reverse reaction recombination barriers for both the three- and four-center eliminations have been included for comparison against the average translational energies. All energies are in units of .

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/content/aip/journal/jcp/130/4/10.1063/1.3065986
2009-01-26
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Photodissociation of vinyl cyanide at 193 nm: Nascent product distributions of the molecular elimination channels
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/4/10.1063/1.3065986
10.1063/1.3065986
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