Ab initio calculations of the structure and inversion barriers of chloramide, H2NCl, and N-chloro-N-methylmethanamine, (CH3)(2)NClстатья
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Аннотация:The ab initio geometries of the equilibrium forms and transition states of the amino nitrogen inversion for H2NCl and (CH3)(2)NCl were calculated by the RHF and MP2 methods with the use of the 6-31G*, 6-31G**, and 6-311G** basis sets. The inclusion of electron correlation at the MP2 level increases the barrier height estimates and yields a somewhat better agreement between the calculated and experimental geometric parameters. The obtained data do not agree with the idea that a larger inversion barrier is associated with a more pyramidal configuration of the nitrogen atom Methyl substituents flatten the nitrogen configuration in (CH3)(2)NCl. The barrier heights calculated by the MP2 method are 10.2 kcal mol(-1) for H2NCl and 12.6 kcal mol(-1) for (CH3)(2)NCl, or 9.3(1.0) and 12.0 (1.0) kcal mol(-1), respectively, when zero-point corrections are made. (C) 1997 Elsevier Science B.V.