科研之友
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摘要
The reactions between ground-state oxygen atoms (O(P-3)) and the ammonia (NH3) and hydrazine (N2H4) molecules have been Studied using electronic-structure and dynamics calculations. Ab initio calculations have been used to characterize the primary reaction channels accessible at hyperthermal energies. These reaction channels are i) hydrogen abstraction, O + NH3(N2H4) -> OH + NH2(N2H3), ii) H-elimination O + NH3(N2H4) -> H + ONH2(ON2H3) and iii) N-N breakage (in the reaction involving hydrazine), O + N2H4 -> ONH2 + NH2 Hydrogen abstraction is the lowest-barrier process, followed by N-N breakage and H-elimination. Comparison of Our highest-accuracy calculations (CCSD(T)/CBS//MP2/aug-cc-pVDZ) with a variety of lower-cost electronic-structure methods shows that the BHandHLYP method, in combination with the 6-31G* basis set, captures remarkably well the essential features of the potential-energy surface of all Of the reaction channels Investigated in this work, Using directly the BHandHLYP/6-31G* combination, we have propagated quasiclassical trajectories to characterize the dynamics of the O + NH3 and O + N2H4 reactions ill hyperthermal energies. The trajectory calculations reveal that hydrogen abstraction is the dominant reaction channel, with cross sections between I factor of 2 and all order of magnitude larger than those for the H-elimination and N-N breakage channels. The dynamics calculations also indicate that most of the energy is partitioned into products relative translation but Significant vibrational excitation of products is possible its well. Analysis of angular distributions and opacity functions suggests that whereas the hydrogen-abstraction reactions proceed through a mechanism with it substantial component of stripping dynamics, H-elimination and N-N breakage are dominated by rebound dynamics.
- 出版日期2009-12-17
- 单位美国弗吉尼亚理工大学(Virginia Tech)
