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论文类型：期刊论文

发表时间：2013-07-15

发表刊物：JOURNAL OF COMPUTATIONAL CHEMISTRY

收录刊物：SCIE、EI、Scopus

卷号：34

期号：19

页面范围：1686-1696

ISSN号：0192-8651

关键字：potential energy surface; ab initio; double many-body expansion; CBS limit

摘要：An accurate single-sheeted double many-body expansion potential energy surface is reported for the title system. A switching function formalism has been used to warrant the correct behavior at the H2(X1 sigma g+)+N(2D) and NH(X3 sigma-)+H(2S) dissociation channels involving nitrogen in the ground N(4S) and first excited N(2D) states. The topographical features of the novel global potential energy surface are examined in detail, and found to be in good agreement with those calculated directly from the raw ab initio energies, as well as previous calculations available in the literature. The novel surface can be using to treat well the Renner-Teller degeneracy of the 12A and 12A states of NH2. Such a work can both be recommended for dynamics studies of the N(2D)+H2 reaction and as building blocks for constructing the double many-body expansion potential energy surface of larger nitrogen/hydrogen-containing systems. In turn, a test theoretical study of the reaction N(2D)+H2(X1 sigma g+)(=0,j=0)NH(X3 sigma-)+H(2S) has been carried out with the method of quantum wave packet on the new potential energy surface. Reaction probabilities, integral cross sections, and differential cross sections have been calculated. Threshold exists because of the energy barrier (68.5 meV) along the minimum energy path. On the curve of reaction probability for total angular momentum J=0, there are two sharp peaks just above threshold. The value of integral cross section increases quickly from zero to maximum with the increase of collision energy, and then stays stable with small oscillations. The differential cross section result shows that the reaction is a typical forward and backward scatter in agreement with experimental measurement result. (c) 2013 Wiley Periodicals, Inc.