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: 3.16). 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.

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