Theoretical and Computational Chemistry

Size dependence of electronic spectrum for H-capped carbon chains, H-(C≡C)n-H: Analysis of its nature and prediction for carbyne

Authors

  • Jiaojiao Wang Jiangsu University of Science and Technology ,
  • Zeyu Liu Jiangsu University of Science and Technology ,
  • Qing Zhou Jiangsu University of Science and Technology ,
  • Tian Lu Beijing Kein Research Center for Natural Sciences ,
  • Xia Wang Jiangsu University of Science and Technology ,
  • Xiufen Yan Jiangsu University of Science and Technology ,
  • Mengdi Zhao Suzhou University of Science and Technology ,
  • Aihua Yuan Jiangsu University of Science and Technology

Abstract

The electronic spectrum of carbon chains has not been well understood in nature and deserves further study. In the present work, (time-dependent) density functional theory [(TD-)DFT] was employed to investigate the geometric and electronic structures as well as the allowed 11Σu+ ← X1Σg+ electronic transition of the H-capped carbon chains H-(C≡C)n-H (n = 3-9). The calculated geometric parameters and vertical excitation energy are perfectly consistent with the known experimental observations. The size dependence of electronic and optical characteristics in carbon chains is explained in depth by wavefunction analysis for electronic excitation and paid special attention to through data fitting and extrapolation, whose accuracy is confirmed by the specified species with n = 15. The suggested extrapolation formulas allow estimating the behavior of the electronic and optical properties for increasing chain length and even obtaining the limit values for sp-hybridized carbon allotrope carbyne.

Content

Thumbnail image of Manuscript.pdf

Supplementary material

Thumbnail image of Supporting Information.pdf
Supporting Information
Optimized Cartesian coordinates (in Å) of the carbon chains H-(C≡C)n-H (n = 3-9, 15) at the ωB97XD/def2-TZVP level, indices of two sets of π MOs of the carbon chains H-(C≡C)n-H (n = 3-9), color-filled contour maps of LOL-y of the carbon chains H-(C≡C)n-H (n = 3-9) on the plane containing the chains, BLA of the carbon chains H-(C≡C)n-H (n = 3-9).