Matter and Radiation at Extremes, Volume. 8, Issue 5, 058402(2023)

Triggering dynamics of acetylene topochemical polymerization

Xingyu Tang1,*... Xiao Dong2, Chunfang Zhang3, Kuo Li1, Haiyan Zheng1 and Ho-kwang Mao1 |Show fewer author(s)
Author Affiliations
  • 1Center for High Pressure Science and Technology Advanced Research, Beijing 100193, People’s Republic of China
  • 2Key Laboratory of Weak-Light Nonlinear Photonics, School of Physics, Nankai University, Tianjin 300071, People’s Republic of China
  • 3College of Chemistry and Materials Science, Hebei University, Baoding 071002, People’s Republic of China
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    Figures & Tables(7)
    Optimized crystal structure of C2H2 at (a) 0 GPa and (b) 25 GPa. (c) Relative changes in unit cell parameters. (d) Selected dC⋯C and (e) angles in the crystal as functions of pressure. d1 is dC⋯C on the a–c plane, and d2 is dC⋯C almost on the a–b plane. ∠1 or ∠2 is the angle between the c axis and the line between two carbon/hydrogen atoms, and ∠3 is the H–C–C bond angle.
    Electronic properties of the intermolecular C⋯C bond vs bond length. The bonding proceeds in three stages. At about 2.3 Å, the Mayer bond order (black) and the ELF value at the midpoint of the bond (red) sharply increase, suggesting the onset of bonding.
    Phonon spectra of the acetylene crystal and some of the vibrational modes at the Γ-point. (a) Spectrum of the optimized structure at 29 GPa. (b) Four phonon branches with imaginary frequencies from the Γ-point to the T-point (0.5, 0, −0.5) at 29 GPa. (c) Spectrum at 0 GPa (experimental 5.7 GPa). In the high-frequency part, the phonon dispersion curves are nearly horizontal. (d) Illustrations of two typical lattice vibrations leading to a decrease in dC⋯C, originating from molecular translations and rotations.
    Vibrational displacement of carbon atoms from the equilibrated position with T-point symmetry applied. The instantaneous dC⋯C at RT becomes 2.3 Å and reaches the threshold for intermolecular bonding.
    Reaction curve from acetylene to polyacetylene in the crystal. The MEP is shown as the black line, and the pathway through the transient “threshold model” is shown as the red line. The left part of each curve describes the enthalpy change of the supercell as the instantaneous dC⋯C varies until intermolecular bonding occurs. The right part is the subsequent reaction displayed in steps. The bonding stage on the new path is rescaled for clarity. Three representative structures along the constructed path are illustrated. The enthalpies of the “threshold model” and the “TS” are almost the same.
    • Table 1. Intermolecular threshold distances for PIP at RT without correction of thermal fluctuation given by experiments.

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      Table 1. Intermolecular threshold distances for PIP at RT without correction of thermal fluctuation given by experiments.

      Molecular crystald(C⋯C)min (Å)Pressure (GPa)Functional group
      Acetylene (C2H2)173.15.7Alkynyl
      Acetylene dicarboxylic acid 3.18
      (HOOC–C≡C–COOH)5
      Monosodium acetylide 2.911
      (NaHC2)18
      1-propargyl-4-amino-3,3.311.3
      5- dinitropyrazole19
      Benzene (C6H6)202.818Phenyl
      Benzene–hexafluorobenzene 2.820
      (C6H6–C6F6)21
      1,4-diphenylbutadiyne 3.210Alkynyl-phenyl
      (DPB)22
      1,3,5-triethynylbenzene 3.44
      (TEB)23
    • Table 2. Phonon frequencies of the lattice vibrational modes at the T-point and the maximum displacements of carbon atoms in the optimized structure at 0 GPa (experimental 5.7 GPa). Displacements are displayed as projections on the coordinate axes.

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      Table 2. Phonon frequencies of the lattice vibrational modes at the T-point and the maximum displacements of carbon atoms in the optimized structure at 0 GPa (experimental 5.7 GPa). Displacements are displayed as projections on the coordinate axes.

      Displacement of a carbon atom (Å)
      Vibrational modeNo.Frequency (cm−1)ΔxΔyΔz
      Translational11130.10300
      21460.08000
      9113000.103
      10189000.062
      Total = ∑Δx, Δy  or Δz0.18300.165
      Librational131650.06400
      141460.07300
      1723800.0270.035
      1814600.0450.058
      Total = ∑Δx, Δy or  Δz0.1370.0720.093
      Total displacement in a–c plane0.411
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    Xingyu Tang, Xiao Dong, Chunfang Zhang, Kuo Li, Haiyan Zheng, Ho-kwang Mao. Triggering dynamics of acetylene topochemical polymerization[J]. Matter and Radiation at Extremes, 2023, 8(5): 058402

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    Paper Information

    Category: High Pressure Physics and Materials Science

    Received: Mar. 23, 2023

    Accepted: Jul. 2, 2023

    Published Online: Nov. 21, 2023

    The Author Email:

    DOI:10.1063/5.0151609

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