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Finite size effects on aluminum/Teflon reaction channels under combustive environment: A Rice–Ramsperger–Kassel–Marcus and transition state theory study of fluorination
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10.1063/1.3480020
/content/aip/journal/jcp/133/13/10.1063/1.3480020
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/13/10.1063/1.3480020

Figures

Image of FIG. 1.
FIG. 1.

Energy level diagram for reaction channel I. Dotted lines connect the transition states with the reactants and the products in each step. The reaction barriers and reaction enthalpies are provided for each step. The value in green is for single-point calculation at the level for the first fluorination step.

Image of FIG. 2.
FIG. 2.

Energy level diagram for reaction channel II. Dotted lines connect the transition states with the reactants and the products in each step. The reaction barriers and reaction enthalpies are provided for each step. The value in green is for single-point calculation at the level for the first fluorination step.

Image of FIG. 3.
FIG. 3.

Energy level diagram for reaction channels III and IV. Dotted lines connect the transition states with the reactants and the products in each step. The reaction barriers and reaction enthalpies are provided for each step. The value in green is for single-point calculation at the level for the first fluorination step.

Image of FIG. 4.
FIG. 4.

Arrhenius plots for the first fluorination step in reaction channels I–IV within the 500–900 K temperature range. Note that adduct formation is kinetically hindered (Fig. 3) and thus may not be the main reaction channel driving the fluorination reaction.

Image of FIG. 5.
FIG. 5.

Calculated energy-dependent RRKM rate constants, , for the first fluorination reaction of channels I–IV.

Image of FIG. 6.
FIG. 6.

Calculated pressure-dependent rates for (a) ; (b) ; (c) ; (d) using model 1, solid trace, and model 2 with , dashed-dot trace, for the master equation calculations (see text). High-pressure limit rates are indicated by arrows with the corresponding numerical value. The formation of the initial complex, , has an energy barrier of 8.4 kcal/mol. Although the rates plotted in panel (d) suggest that the reaction is the fastest, the kinetically hindered formation of the initial complex may render this reaction comparable to the COF channel.

Image of FIG. 7.
FIG. 7.

Plot of the molecular orbital density , HOMO, LUMO, and of the , , , , and clusters calculated at the PBE0/6-311G(d) level.

Tables

Generic image for table
Table I.

The calculated atomic charges from CHeLpG population analysis at the PBE0/6-311G(d) level of theory.

Generic image for table
Table II.

The calculated , , gaps, and the respective energy barriers along four reactions channels .

Generic image for table
Table III.

Role of finite size as evident from the comparison of trends in temperature-dependent rate constants performed at CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ and DFT/PBE0/6-311G(d) levels for reactions involving Al atom and Al clusters, respectively. Activation energies are in cal/mol.

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/content/aip/journal/jcp/133/13/10.1063/1.3480020
2010-10-06
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Finite size effects on aluminum/Teflon reaction channels under combustive environment: A Rice–Ramsperger–Kassel–Marcus and transition state theory study of fluorination
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/13/10.1063/1.3480020
10.1063/1.3480020
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