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Experimental and theoretical study of the pyrrole cluster photochemistry: Closing the dissociation pathway by complexation
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10.1063/1.2754687
/content/aip/journal/jcp/127/6/10.1063/1.2754687
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/6/10.1063/1.2754687

Figures

Image of FIG. 1.
FIG. 1.

Schematic view of the cluster photodissociation experiment.

Image of FIG. 2.
FIG. 2.

(a) The mass spectrum of clusters produced in He expansions at , , and 0.33% concentration of Py in He. The mean neutral cluster size under these conditions was . (b) The mass spectrum of clusters produced in Ar expansions at , , and 0.16% concentration of Py in Ar, where the mean cluster size could not be determined exactly but it was (see Ref. 45 for details). Gray bars correspond to clusters.

Image of FIG. 3.
FIG. 3.

Measured TOF distribution of H fragments from the photolysis of pyrrole clusters produced (a) in He expansions corresponding to the mean cluster size and (b) in Ar expansions corresponding to the mean cluster size for two different laser polarizations of 0° and 90° at .

Image of FIG. 4.
FIG. 4.

H-fragment kinetic energy distributions from the photolysis of pyrrole clusters produced in He expansions for two different laser polarizations of 0° and 90° at . The KEDs were obtained by fitting the TOF spectra from Fig. 3(a) corresponding to the mean cluster size .

Image of FIG. 5.
FIG. 5.

Comparison of H-fragment KEDs from the photolysis at of (a) pyrrole molecule, (b) clusters with produced in He expansions, and (c) clusters with produced in Ar expansions.

Image of FIG. 6.
FIG. 6.

Ratio of fast (F) and slow (S) channel fragments for different mean cluster sizes and two laser polarizations.

Image of FIG. 7.
FIG. 7.

Measured TOF distribution of H fragments from photolysis at of (a) pyrrole clusters produced in He expansions corresponding to the mean cluster size and (b) the corresponding KED.

Image of FIG. 8.
FIG. 8.

Calculated geometries of the Franck-Condon point, the and crossings, and the H-transfer structure. Relative energies with respect to the Py ground state are indicated. The energies of the lowest Rydberg state and the lowest valence state are shown for the Franck-Condon point. Energies were calculated at the level (for H-transfer structure diffuse functions were placed on all atoms).

Image of FIG. 9.
FIG. 9.

Potential energy curves along the rigid N–H stretching coordinate for bare (right panel) and solvated (left panel) pyrrole molecules. Energies are calculated at the level.

Image of FIG. 10.
FIG. 10.

Linear interpolation between the ground state geometry and the intersection for the bare pyrrole molecule (right panel) and the molecule solvated by an argon atom (left panel). Energies were calculated at the level. Interpolation index corresponds to the ground state geometry and interpolation index to the conical intersection.

Image of FIG. 11.
FIG. 11.

Important structures on the potential energy surface of the pyrrole dimer together with the respective linear interpolation potential energy curves. The presented relative energies are in eV and are calculated at the level; for H-transfer structure the basis is further augmented with diffuse functions on nitrogens and transferred hydrogen. Relative energies with respect to the ground state energy are shown. The energies of the lowest Rydberg state and the lowest valence state are shown for the Franck-Condon structure. Linear interpolation between the ground state structure and out-of-plane intersection (structure B) is shown in panel (a), interpolation between the ground state structure and chemically bound pyrrole dimer is shown in panel (b), and interpolation between the ground state structure and hydrogen transfer structure is shown in panel (c). Another reaction channel (not shown) is the N–H fission in the state feasible for the free N–H bond but closed for the arrangement. Interpolation index corresponds to the ground state geometry and interpolation index to the final structures (conical intersection, dimer, hydrogen transfer molecule).

Image of FIG. 12.
FIG. 12.

Schematic figure showing the influence of the solvent on the photochemistry of pyrrole. The upper panel shows the situation for the bare Py molecule (partly adopted from Ref. 23) and the lower panel illustrates the effect of solvation in the N–H bond stretching and ring deformation coordinates.

Tables

Generic image for table
Table I.

Experimental conditions.

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/content/aip/journal/jcp/127/6/10.1063/1.2754687
2007-08-13
2014-04-16
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Experimental and theoretical study of the pyrrole cluster photochemistry: Closing the πσ* dissociation pathway by complexation
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/6/10.1063/1.2754687
10.1063/1.2754687
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