A Quantum Wave Packet Dynamics Study of the N(²D) + H₂ Reaction

Abstract

We report a dynamics study of the reaction N((2)D) + H(2) (v=0, j=0-5) --> NH + H using the time-dependent quantum wave packet method and a recently reported single-sheeted double many-body expansion potential energy surface for NH(2)(1(2)A' ') which has been modeled from accurate ab initio multireference configuration-interaction calculations. The calculated probabilities for (v=0, j=0-5) are shown to display resonance structures, a feature also visible to some extent in the calculated total cross sections for (v=0, j=0). A comparison between the calculated centrifugal-sudden and coupled-channel reaction probabilities validate the former approximation for the title system. Rate constants calculated using a uniform J-shifting scheme and averaged over a Boltzmann distribution of rotational states are shown to be in good agreement with the available experimental values. Comparisons with other theoretical results are also made.

Accurate double many‐body expansion potential energy surface by extrapolation to the complete basis set limit and dynamics calculations for ground state of NH2

“… is a well‐established prototype for the study of insertion reactions, with the reaction also playing a key role in the combustion of nitrogen‐containing materials. During the past decade, the reaction has been much studied both experimentally and theoretically . There are five electronic doublet states correlating with the title reaction, and this reaction is a prototype for studying nonadiabatic effect.…”

Effect of collision energy on cross sections and product alignments for the C(1D) + H2 (v = 0, j = 0) insertion reactions

“…1 The reaction between atomic carbon and molecular hydrogen belongs to this class of insertion reaction. Other thoroughly studied insertion reactions between electronically excited atoms and hydrogen molecules are O( 1 D) + H 2 , 2-7 N( 2 D) + H 2 , [8][9][10] and S( 1 D) + H 2 . [11][12][13][14] Unlike other members of the insertion reaction family, however, C( 1 D) + H 2 is considered to be a clean insertion reaction, 15,16 without involvement of abstraction pathways.…”

Exploring NH (X3Σ−)+D (2S)→N (4S)+HD (X1Σg+) reaction with time-dependent wave packet method

“…In this section, we describe the TDWP method [21][22][23] employed to calculate the initial state-selected total reaction probability of the triatomic reactions. This method is a powerful and economic method for the study of quantum reactive scattering dynamics.…”