1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
Pulsed laser photolysis and quantum chemical-statistical rate study of the reaction of the ethynyl radical with water vapor
Rent:
Rent this article for
USD
10.1063/1.1861887
/content/aip/journal/jcp/122/11/10.1063/1.1861887
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/11/10.1063/1.1861887

Figures

Image of FIG. 1.
FIG. 1.

Experimental time profile of —fitted to a single-exponential function—following dissociation of in the presence of , and at a total pressure of .

Image of FIG. 2.
FIG. 2.

Variation of pseudo-first-order decay rates with at and at a total pressure of .

Image of FIG. 3.
FIG. 3.

Variation of pseudo-first-order decay rates with at and at a total pressure of .

Image of FIG. 4.
FIG. 4.

Variation of pseudo-first-order decay rates with at and at a total pressure of .

Image of FIG. 5.
FIG. 5.

Arrhenius plot of the experimental rate constants (circles) determined for the reaction in the present study. Also shown are our TST calculations [Eq. (9)] applied to the -optimized structures of , , and . The bottom two lines of the key refer to TST calculations using the barrier height calculated at the level with ZPE, the top two lines refer to TST calculations based on the barrier height. For each pair of lines in the key, the upper one refers to calculations that treat the HOHC torsional motion as a vibration , the lower one treats this motion as a hindered internal rotation ( and barrier to rotation of ).

Image of FIG. 6.
FIG. 6.

Schematic potential energy profiles showing the different channels related to the reaction of ethynyl radical with water. Relative energies, in kJ/mol, were obtained using calculations. Selected optimized geometries are also displayed. Bond lengths are given in angstroms and bond angles in degrees.

Image of FIG. 7.
FIG. 7.

Schematic potential energy profiles showing the interconversions between different isomers. Relative energies, in kJ/mol, were obtained using calculations. Selected optimized geometries are also displayed. Bond lengths are given in angstroms and bond angles in degrees.

Image of FIG. 8.
FIG. 8.

Schematic potential energy profiles showing the interconversions between different isomers, in particular the reaction. Relative energies, in kJ/mol, were obtained using calculations. Selected optimized geometries are also displayed. Bond lengths are given in angstroms and bond angles in degrees.

Image of FIG. 9.
FIG. 9.

Geometry of the transition structure for hydrogen abstraction of the reaction using different levels of theory. Entries are (upper), , , and (lower). Bond lengths are given in angstroms and bond angles in degrees.

Tables

Generic image for table
Table I.

Relative energies (kJ/mol) of all stationary points considered at two levels of theory.

Generic image for table
Table II.

Calculated total energy (hartree), zero-point energy (kJ/mol), and relative energy (kJ/mol) of the , , and TS abstraction .

Generic image for table
Table III.

Calculated vibrational frequencies for the critical species at the level of theory.

Generic image for table
Table IV.

Transition-state-theory calculations of the rate constant for the reaction based on or CASSPT2/CASSCF single-point energies and critical structures computed at the level.

Loading

Article metrics loading...

/content/aip/journal/jcp/122/11/10.1063/1.1861887
2005-03-18
2014-04-24
Loading

Full text loading...

This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Pulsed laser photolysis and quantum chemical-statistical rate study of the reaction of the ethynyl radical with water vapor
http://aip.metastore.ingenta.com/content/aip/journal/jcp/122/11/10.1063/1.1861887
10.1063/1.1861887
SEARCH_EXPAND_ITEM