Dynamics of the insertion reaction C(<sup>1</sup>D) + H<sub>2</sub>: A comparison of crossed molecular beam experiments with quasiclassical trajectory and quantum mechanical scattering calculations

The H + +D 2 → HD+ D + reaction has been theoretically investigated by means of an exact quantum mechanical approach, a quasiclassical trajectory method, and two statistical methods based in the propagation of either wave functions or trajectories. The study addresses the possible changes on the overall dynamics of the title reaction when the D 2 diatom is rotationally excited to its v =0, j =1 state. In addition, the reactivity for the ground rotational state on two different potential energy surfaces ͑PESs͒, namely, the surface by Aguado et al. ͓J. Chem. Phys. 112, 1240 ͑2000͔͒ and the PES by Kamisaka et al. ͓J. Chem. Phys. 116, 654 ͑2002͔͒, is examined. Reaction probabilities and cross sections at 0.524 and 0.1 eV collision energies are calculated. The major differences with respect to the reaction initiated with D 2 in its ground rovibrational state are observed for the lowest collision energy E c = 0.1 eV. Differential cross sections have been found to depend to some extend on the PES employed. In addition, at E c = 0.1 eV further discrepancies in the total and rotational cross sections are noticeable.

Section: Discussionmentioning

confidence: 98%

Effects of the rotational excitation of D2 and of the potential energy surface on the H++D2→HD+D+ reaction

González‐Lezana

Honvault

Jambrina

et al. 2009

“…These results have served as accurate benchmarks for dynamical studies of complex-forming reactions, featuring barrierless reaction pathways through deep potential wells. [5][6][7][8][9] However, due to the N 3 ͑N is the number of basis functions͒ scaling law in the formalism, it is extremely difficult to extend the TID-CC method to calculate cross sections for more complex systems, such the H + O 2 reaction, which possesses a deep well and two heavy ͑nonhydrogen͒ atoms. 10 On the other hand, the TDWP method scales more favorably than the TID-CC method in both memory and the number of arithmetic operations because the basic operation involves matrix-vector multiplication.…”

Section: Introductionmentioning

confidence: 99%

Extraction of state-to-state reactive scattering attributes from wave packet in reactant Jacobi coordinates

Sun

Guo

Zhang

2010

138

126

The S-matrix for a scattering system provides the most detailed information about the dynamics. In this work, we discuss the calculation of S-matrix elements for the A + BC→ AB+ C, AC+ B type reaction. Two methods for extracting S-matrix elements from a single wave packet in reactant Jacobi coordinates are reviewed and compared. Both methods are capable of extracting the state-to-state attributes for both product channels from a single wave packet propagation. It is shown through the examples of H + HD, Cl+ H 2 , and H + HCl reactions that such reactant coordinate based methods are easy to implement, numerically efficient, and accurate. Additional efficiency can be gained by the use of a L-shaped grid with two-dimensional fast Fourier transform.

“…As expected, this reaction is ideally suited for statistical treatments, and most of its dynamics is very well reproduced by the SQM model. 13,16,23,43 In what follows a comparison between SQCT and SQM results will be shown for this reaction.…”

Section: A C" 1 D… +H 2 Reactionmentioning

confidence: 99%

“…13 The corresponding ICS into vЈ =0, jЈ are shown in Fig. 1 at these collision energies and initial states.…”

Section: A C" 1 D… +H 2 Reactionmentioning

confidence: 99%

A comparison of quantum and quasiclassical statistical models for reactions of electronically excited atoms with molecular hydrogen

Aoiz

González‐Lezana

Rábanos

2008

A detailed comparison of statistical models based on the quasiclassical trajectory ͑SQCT͒ and quantum mechanical ͑SQM͒ methods is presented in this work for the C͑ 1 D͒ +H 2 , S͑ 1 D͒ +H 2 , O͑ 1 D͒ +H 2 and N͑ 2 D͒ +H 2 insertion reactions. Reaction probabilities, integral ͑ICS͒ and differential ͑DCS͒ cross sections at different levels of product's state resolution are shown and discussed for these reactions. The agreement is in most cases excellent and indicates that the effect of tunneling through the centrifugal barrier is negligible. However, if there exists a dynamical barrier, as in the case of the N͑ 2 D͒ +H 2 reaction, some of the SQM results can be slightly different than those calculated with the SQCT model. The rationale of the observed similarities and discrepancies can be traced back to the specific topologies of the potential energy surfaces for each of the reactions examined. The SQCT model is sensitive enough to show the relatively small inaccuracies resulting from the decoupling inherent to the centrifugal sudden approximation when used in the SQM calculations. In addition, the effect of ignoring the parity conservation is also examined. This effect is in general minor except in particular cases such as the DCS from initial rotational state j =0, which requires, in order to reproduce the sharp forward and backward peaks, the explicit conservation of parity.