### Abstract

A detailed theoretical study of geometric, electronic, vibrational, and spec-troscopic properties of linear carbon chains is presented. The study is supplemented with an extensive survey of available experimental and theo-retical results. Our calculations constitute a bridge between the quantum-chemical and solid-state simulations, using the SCC-DFTB (self-consistent-charge density-functional tight-binding) methodology. The computed equi-librium geometry, electronic band structure, and phonon dispersion curves of infinite carbon chains are compared with analogous results obtained for finite oligomers. A surprisingly fast convergence of all the studied properties of the finite systems to the infinite limit and a rather short-ranged influence of the terminal sections of the chain are observed. The molecular calculations display analogues of well known solid state physics phenomena, such as Peierls distortion or Kohn anomaly. The presented IR and Raman spectra of finite chains show that the infinite limit is approached rapidly both in the frequency and intensity domain. For a constant mass sample, the intensity of the IR signal is inversely proportional to the number of carbons atoms in the chain, while the intensity of the main Raman band becomes independent on the chain length. The satellite bands and terminal group vibrations disappear from the Raman spectra already for relatively short chains.

Original language | English |
---|---|

Title of host publication | Spectroscopy, Dynamics and Molecular Thoery of Carbon Plasmas and Vapors |

Subtitle of host publication | Advances in the Understanding of the Most Complex High-Temperature Elemental System |

Publisher | World Scientific Publishing Co. |

Pages | 375-415 |

Number of pages | 41 |

ISBN (Electronic) | 9789812837653 |

ISBN (Print) | 9812837647, 9789812837646 |

DOIs | |

Publication status | Published - 2011 Jan 1 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Biochemistry, Genetics and Molecular Biology(all)
- Chemistry(all)
- Engineering(all)

### Cite this

*Spectroscopy, Dynamics and Molecular Thoery of Carbon Plasmas and Vapors: Advances in the Understanding of the Most Complex High-Temperature Elemental System*(pp. 375-415). World Scientific Publishing Co.. https://doi.org/10.1142/9789812837653_0012

**Vibrational spectroscopy of linear carbon chains.** / Chou, Chien Pin; Li, Wun Fan; Witek, Henryk A.; Andrzejak, Marcin.

Research output: Chapter in Book/Report/Conference proceeding › Chapter

*Spectroscopy, Dynamics and Molecular Thoery of Carbon Plasmas and Vapors: Advances in the Understanding of the Most Complex High-Temperature Elemental System.*World Scientific Publishing Co., pp. 375-415. https://doi.org/10.1142/9789812837653_0012

}

TY - CHAP

T1 - Vibrational spectroscopy of linear carbon chains

AU - Chou, Chien Pin

AU - Li, Wun Fan

AU - Witek, Henryk A.

AU - Andrzejak, Marcin

PY - 2011/1/1

Y1 - 2011/1/1

N2 - A detailed theoretical study of geometric, electronic, vibrational, and spec-troscopic properties of linear carbon chains is presented. The study is supplemented with an extensive survey of available experimental and theo-retical results. Our calculations constitute a bridge between the quantum-chemical and solid-state simulations, using the SCC-DFTB (self-consistent-charge density-functional tight-binding) methodology. The computed equi-librium geometry, electronic band structure, and phonon dispersion curves of infinite carbon chains are compared with analogous results obtained for finite oligomers. A surprisingly fast convergence of all the studied properties of the finite systems to the infinite limit and a rather short-ranged influence of the terminal sections of the chain are observed. The molecular calculations display analogues of well known solid state physics phenomena, such as Peierls distortion or Kohn anomaly. The presented IR and Raman spectra of finite chains show that the infinite limit is approached rapidly both in the frequency and intensity domain. For a constant mass sample, the intensity of the IR signal is inversely proportional to the number of carbons atoms in the chain, while the intensity of the main Raman band becomes independent on the chain length. The satellite bands and terminal group vibrations disappear from the Raman spectra already for relatively short chains.

AB - A detailed theoretical study of geometric, electronic, vibrational, and spec-troscopic properties of linear carbon chains is presented. The study is supplemented with an extensive survey of available experimental and theo-retical results. Our calculations constitute a bridge between the quantum-chemical and solid-state simulations, using the SCC-DFTB (self-consistent-charge density-functional tight-binding) methodology. The computed equi-librium geometry, electronic band structure, and phonon dispersion curves of infinite carbon chains are compared with analogous results obtained for finite oligomers. A surprisingly fast convergence of all the studied properties of the finite systems to the infinite limit and a rather short-ranged influence of the terminal sections of the chain are observed. The molecular calculations display analogues of well known solid state physics phenomena, such as Peierls distortion or Kohn anomaly. The presented IR and Raman spectra of finite chains show that the infinite limit is approached rapidly both in the frequency and intensity domain. For a constant mass sample, the intensity of the IR signal is inversely proportional to the number of carbons atoms in the chain, while the intensity of the main Raman band becomes independent on the chain length. The satellite bands and terminal group vibrations disappear from the Raman spectra already for relatively short chains.

UR - http://www.scopus.com/inward/record.url?scp=84971011070&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84971011070&partnerID=8YFLogxK

U2 - 10.1142/9789812837653_0012

DO - 10.1142/9789812837653_0012

M3 - Chapter

SN - 9812837647

SN - 9789812837646

SP - 375

EP - 415

BT - Spectroscopy, Dynamics and Molecular Thoery of Carbon Plasmas and Vapors

PB - World Scientific Publishing Co.

ER -