• Matter and Radiation at Extremes
  • Vol. 8, Issue 5, 058402 (2023)
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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    DOI: 10.1063/5.0151609 Cite this Article
    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 Copy Citation Text show less

    Abstract

    Topochemical reactions are a promising method to obtain crystalline polymeric materials with distance-determined regio- or stereoselectivity. It has been concluded on an empirical basis that the closest intermolecular C⋯C distance in crystals of alkynes, d(C⋯C)min, should reach a threshold of ∼3 Å for bonding to occur at room temperature. To understand this empirical threshold, we study here the polymerization of acetylene in the crystalline state under high pressure by calculating the structural geometry, vibrational modes, and reaction profile. We find d(C⋯C)min to be the sum of an intrinsic threshold of 2.3 Å and a thermal displacement of 0.8 Å (at room temperature). Molecules at the empirical threshold move via several phonon modes to reach the intrinsic threshold, at which the intermolecular electronic interaction is sharply enhanced and bonding commences. A distance–vibration-based reaction picture is thus demonstrated, which provides a basis for the prediction and design of topochemical reactions, as well as an enhanced understanding of the bonding process in solids.
    x2=kBTM(2πcν)2,

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    iNatoms12mixi,j,max2=kBT(2πcνj)2,

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    xC,max=jxC,j,max.

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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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