New ab initio potential energy surface and quantum dynamics of the reaction H(2S) + NH(X3Σ-) → N(4S) + H2.

State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
The Journal of Chemical Physics (Impact Factor: 3.12). 09/2011; 135(10):104314. DOI: 10.1063/1.3636113
Source: PubMed

ABSTRACT A new global potential energy surface is reported for the ground state ((4)A(")) of the reaction H((2)S) + NH(X(3)Σ(-)) → N((4)S) + H(2) from a set of accurate ab initio data, which were computed using the multi-reference configuration interaction with a basis set of aug-cc-pV5Z. The many-body expansion and neural network methods have been used to construct the new potential energy surface. The topographical features of the new global potential energy surface are presented. The predicted barrier height is lower than previous theoretical estimates and the heat of reaction with zero-point energy is closer to experimental results. The quantum reactive scattering dynamics calculation was carried out over a range of collision energies (0-1.0 eV) on the new potential energy surface. The reaction probabilities, integral cross-section, and rate constants for the title reaction were calculated. The calculated rate constants are in excellent agreement with the available experimental results.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: 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(X1Σg+)+N(2D) and NH (X3Σ-)+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 NH 2. 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(X1Σg+)(ν=0,j=0)→NH (X3Σ-)+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. © 2013 Wiley Periodicals, Inc.
    Journal of Computational Chemistry 05/2013; 34:1686. · 3.60 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: The quasi-classical trajectory (QCT) is calculated to study the stereodynamics properties of the title reaction H(2S) + NH(X3 Σ−) → N(4S) + H2 on the ground state 4A'' potential energy surface (PES) constructed by Zhai and Han [2011 J. Chem. Phys. 135 104314]. The calculated QCT reaction probabilities and cross sections are in good agreement with the previous theoretical results. The effects of the collision energy on the k—k' distribution and the product polarization of H2 are studied in detail. It is found that the scattering direction of the product is strongly dependent on the collision energy. With the increase in the collision energy, the scattering directions of the products change from backward scattering to forward scattering. The distribution of P(θr) is strongly dependent on the collision energy below the lower collision energy (about 11.53 kcal/mol). In addition, the P(r) distribution dramatically changes as the collision energy increases. The calculated QCT results indicate that the collision energy plays an important role in determining the stereodynamics of the title reaction.
    Chinese Physics B 06/2013; 22(6):068201. · 1.39 Impact Factor