中国物理B ›› 2022, Vol. 31 ›› Issue (12): 123101-123101.doi: 10.1088/1674-1056/ac9b04

所属专题: SPECIAL TOPIC — The third carbon: Carbyne with one-dimensional sp-carbon

• • 上一篇    下一篇

Chemical bonding in representative astrophysically relevant neutral, cation, and anion HCnH chains

Ioan Baldea   

  1. Theoretical Chemistry, Heidelberg University, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany
  • 收稿日期:2022-05-27 修回日期:2022-09-26 接受日期:2022-10-18 出版日期:2022-11-11 发布日期:2022-12-05
  • 通讯作者: Ioan Baldea E-mail:ioan.baldea@pci.uni-heidelberg.de
  • 基金资助:
    The author thanks Jochen Schirmer for valuable discussions. The author gratefully acknowledges financial support from the German Research Foundation (DFG Grant No. BA 1799/3-2) in the initial stage of this work and computational support by the state of Baden-Wurttemberg through bwHPC and the German Research Foundation through Grant No. INST 40/575-1 FUGG (bwUniCluster 2.0, bwForCluster/MLS&WISO 2.0/HELIX, and JUSTUS 2.0 cluster).

Chemical bonding in representative astrophysically relevant neutral, cation, and anion HCnH chains

Ioan Baldea   

  1. Theoretical Chemistry, Heidelberg University, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany
  • Received:2022-05-27 Revised:2022-09-26 Accepted:2022-10-18 Online:2022-11-11 Published:2022-12-05
  • Contact: Ioan Baldea E-mail:ioan.baldea@pci.uni-heidelberg.de
  • Supported by:
    The author thanks Jochen Schirmer for valuable discussions. The author gratefully acknowledges financial support from the German Research Foundation (DFG Grant No. BA 1799/3-2) in the initial stage of this work and computational support by the state of Baden-Wurttemberg through bwHPC and the German Research Foundation through Grant No. INST 40/575-1 FUGG (bwUniCluster 2.0, bwForCluster/MLS&WISO 2.0/HELIX, and JUSTUS 2.0 cluster).

摘要: Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.

关键词: astrophysics, interstellar medium (ISM), carbon chains, Wiberg and Mayer bond order indices

Abstract: Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.

Key words: astrophysics, interstellar medium (ISM), carbon chains, Wiberg and Mayer bond order indices

中图分类号:  (Theory of electronic structure, electronic transitions, and chemical binding)

  • 31.10.+z
33.15.Fm (Bond strengths, dissociation energies) 36.40.-c (Atomic and molecular clusters)