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The Rate Constants And Product Ratios

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3.2 Rate Constants and Product Ratios
As mentioned above, the initial addition (CHClBr+NO2→ CHClBrNO2 a) is barrierless and extremely exothermic. Considering the lower energy barriers for subsequent reactions, a, once formed, will isomerize or dissociate to the products. The energy information in the initial addition process is critically important for such case in the kinetic calculations. However, IRC calculation can not be conducted for the barrierless reaction. Since the electronic interaction between C in CHClBr and N in NO2 plays a significant role in this process, the energy profile of the association can be obtained by the relaxed scan, in which the C-N distance in a is fixed from r=2.2 to 3.6 Å in a step size of 1.0 Å and remaining geometries are optimized at B3LYP/6-31+G(d) level using tight convergence criteria. Subsequently, CASPT2 method is utilized to calculate the single point energies. Here, the energy of the reactants at r=10 Å are set to be zero for CASPT2 method. In order to account for the dynamic electron correlation, the CASPT2(16,11)/aug-cc-pVTZ energies are scaled by a factor of 1.18, corresponding to the ratio of the dissociation energies of a calculated at CCSD(T)/6-311++G(d,p) level (-45.17 kcal/mol) and the CASPT2(16,11)/aug-cc-pVTZ level (38.29 kcal/mol). Both of the results with ZPE correction are shown in Figure 3. Figure 3 confirmed our assumption that a is formed barrierlessly via carbon-to-nitrogen approach. Based on the energy information

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