Experimental and theoretical study of the recombination reaction F + FC(O)O + M → FC(O)OF + M

Theoretical study of the thermochemistry and the kinetics of the SF Cl (x= 0–5) series

“…SF 5 + Cl are listed in Table 8. The calculated f rigid factors are in the normal range of values expected for reactions of atom + polyatomic radicals and exhibit small temperature dependencies [26,44,45]. The reduction observed in f rigid with the mayor radical complexity is determined by the interplay established along the reaction coordinate, between the increase of the rovibrational adiabatic energy of the transitional channels and the decrease of the electronic potential energy [26,46].…”

“…The SACM/CT model is well documented, such that details of the calculations are omitted for simplicity [26]. Moreover, detailed theoretical studies for the association reactions of FC(O)O radicals with F [44] and Cl [45] atoms can be found elsewhere. The required molecular parameters were extracted (vibrational frequencies and energetics) or calculated (rotational constants) from the data listed in Tables 1 and 2.…”

Theoretical kinetic study of the reaction of SF5 radical with F2, Cl2 and SF5

“…while a standard anisotropy parameter of α/β = 0.5, α = 0.93 Å -1 , (defined as ω = ω e exp(-α(rr e ) [43]) was used to model the evolution of the transitional vibrational frequencies along the minimum energy path. Simplified SACM calculations show that a large number of experimental recombination/dissociation rate coefficients at the high pressure limit can be satisfactorily reproduced using a ratio α/β ≈ 0.5 ± 0.1 [40,[44][45][46][47][48][49][50][51][52][53]. The computed f rigid (T→0) values were afterwards corrected by temperature dependencies: f rigid (T) = f rigid (T→0) [1 -(2.31C eff ) (βr e ) 1/2 exp(X/2.044) with X= ln(k B T/D e )βr e , being r e = 2.4 Å the distance between the center of mass of SF 5 radicals in S 2 F 10 .…”

Quantum chemical study of the atmospheric C2H5C(O)OONO2 (PPN) molecule and of the C2H5C(O)OO and C2H5C(O)O radicals

“…The diffuse functions included in the basis set grant radial flexibility to represent electron density far from the nuclei, while the p, d, and f-type polarization functions confer angular flexibility to represent regions of high electron density among the bonded atoms. In addition, we have also used the G3MP2B3 model chemistry [30] and a modified version that employs for the molecular geometries and vibrational frequencies the functional B3LYP/6-311++G(3df,3pd) instead of standard B3LYP/6-31G(d) [31][32][33][34]. This approach is denoted here as G3MP2// B3LYP/6-311++G(3df,3pd).…”

“…The methodology employed to estimate the enthalpies of formation of PPN, C 2 H 5 C(O)OO, and C 2 H 5 C(O)O is similar to that used in recent publications from this laboratory [25,[31][32][33][34]43]. They were computed from total atomization energies and from isodesmic reaction schemes.…”