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论文类型：期刊论文

发表时间：2018-03-07

发表刊物：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录刊物：SCIE、PubMed

卷号：20

期号：9

页面范围：6638-6647

ISSN号：1463-9076

摘要：The global diabatic potential energy surfaces (PESs) of the MgH2+ system, which can be used to study the dynamics of the Mg+(3p(2)P) + H-2(X-1 Sigma(+)(g)) - MgH+(X-1 Sigma(+)) + H(S-2) reaction, are structured for the first time. The diabatic PESs are correlated with the ground state 1(2)A ' and the first excited state 2(2)A '. The multi-reference configuration interaction method and the VQZ basis set are used in ab initio calculations, and diabatic potential energies are calculated based on the molecular properties of the dipole moment. The neural network method is applied to fit the matrix elements of the diabatic energy surfaces. Spectroscopic constants of H-2(X-1 Sigma(+)(g)) and MgH+(X-1 Sigma(+)) obtained from the new PESs agree well with the experimental data. Based on the diabatic PESs of MgH2+, the time-dependent wavepacket calculations for the Mg+(3p(2)P) + H-2(X-1 Sigma(+)(g)) -> MgH+(X-1 Sigma(+)) + H(S-2) reaction are carried out to study the reaction dynamics. There is no threshold for this reaction because of the existence of barrierless reactive paths. The reaction has a high total integral cross section (ICS), and vibrationally resolved ICSs show an obvious population inversion of product vibrational states. The results of differential cross sections (DCSs) indicate that most product molecules tend to forward scatter.