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Acta Chimica Sinica >

2013 , Vol. 71 >Issue 05: 743 - 748

DOI: https://doi.org/10.6023/A13010049

Article

Mechanism Study of C4H(X2∑+)+H2 Reaction by Direct Ab Initio Methods

  • Huo Ruiping ,
  • Zhang Xiang ,
  • Huang Xuri ,
  • Li Jilai ,
  • Sun Chiachung
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  • a State Key Laboratory of Theoretical & Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China;
    b School of Chemistry and Materials Science, Shanxi Normal University, Linfen 041004, China

Received date: 2013-01-10

  Online published: 2013-03-05

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21103064, 21073075, 21173097), Research Fund for the Doctoral Program of Higher Education of China (No. 20100061110046), the Special Funding of State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Basic Research Fund of Jilin University (Nos. 421010061439, 450060445067) and the Graduate Innovation Fund of Jilin University (20121036).

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Abstract

Hydrogen-deficient molecules have been implicated as the key intermediates in the combustion, planetary atmospheres, and so on. Their reactions with other molecules and/or radicals play important roles and are hot topic in interstellar chemistry. Although extensive efforts have been addressed on the electronic and spectroscopic properties of these molecules, continued extensive research, for example the kinetics and mechanism of their reactions, is still desirable. Therefore, we investigated the hydrogen abstraction (HAT) reaction by the linear butadiynyl radical C4H (CCCCH) from hydrogen (H2) by direct ab initio kinetics over a wide temperature range 40～1000 K theoretically at the CCSD(T)/aug-cc-pVTZ//BB1K/6-311+G(2d,2p) level of theory. The optimized geometries and frequencies of the stationary points are calculated at the BB1K/6-311+G(2d,2p), B3LYP/6-311+G(2d,2p) and M06-2x/6-311+G(2d,2p) level, respectively. To obtain more reliable reaction energies and barrier heights, high-level single-point calculations for the stationary points have been performed at the CCSD(T)/aug-cc-pVTZ by using BB1K/6-311+G(2d,2p) Cartesian coordinates. Two different hydrogen abstraction channels by C1 and C4 of C4H (C1C2C3C4H) have been explored, namely, Channel 1 (R1) and Channel 2 (R2). The activation barrier heights of Channel 1 and Channel 2 are 3.58 kcal/mol and 26.56 kcal/mol, respectively. The results indicate that C1 position of the C4H is a more reactive site. The electron transfer evolution may offer important clues for understanding hydrogen atom transfer (HAT), we therefore analyzed the electron transfer behaviors by NBO in detail. The theoretical rate constants were predicted by the conventional variational transition state theory (VTST), canonical variational transition-state theory (CVT) incorporating a small-curvature tunneling correction (CVT/SCT) method. For the lowest frequency, the partition function is evaluated using the hindered rotor approximation and the other vibrational modes are treated as quantum mechanical separable harmonic oscillators. The overall CVT/SCT rate constants are excellent in agreement with the available experimental results. The three-parameter expressions of Arrhenius rate constants are also provided within 40～1000 K. It is expected to be helpful for future studies over a wide temperature range where no experimental data available so far.

Key words： C4H; H2; rate constant; transition state theory (TST)

Cite this article

Huo Ruiping , Zhang Xiang , Huang Xuri , Li Jilai , Sun Chiachung . Mechanism Study of C4H(X2∑+)+H2 Reaction by Direct Ab Initio Methods[J]. Acta Chimica Sinica, 2013 , 71(05) : 743 -748 . DOI: 10.6023/A13010049

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