Density functional study on the structures and vibrational spectra of the radical anion and cation of biphenyl

Kazuhiko Furuya, Hajime Torii, Yukio Furukawa, Mitsuo Tasumi

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

Density functional theory using the 6-31G* basis set and two non-local exchange-correlation functionals (B-YLP and B3-LYP) has been applied to the calculations of the structures and vibrational spectra of the radical anion and cation, of biphenyl. The B3-LYP dihedral angles between the two phenyl rings are 5.8° and 19.5° for the radical anion and cation, respectively. Upon ionization, structural changes occur in the direction from benzenoid to quinoid. The unscaled vibrational frequencies calculated at the B-YLP/6-31G* level are mostly in agreement with the frequencies in the Raman spectra of the radical anion and cation of the normal and perdeuterated species reported in the literature. The calculations predict that both the radical anion and cation give rise to a very strong infrared band, and that this band arises from a mode in which the benzenoid-to-quinoid deformation occurs out of phase in the two phenyl rings.

Original languageEnglish
Pages (from-to)225-235
Number of pages11
JournalJournal of Molecular Structure: THEOCHEM
Volume424
Issue number3
Publication statusPublished - 1998 Feb 18
Externally publishedYes

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Vibrational spectra
vibrational spectra
Anions
Cations
Negative ions
Positive ions
anions
cations
rings
Dihedral angle
functionals
Ionization
Density functional theory
dihedral angle
Raman scattering
Raman spectra
density functional theory
Infrared radiation
ionization
diphenyl

Keywords

  • Biphenyl
  • Density functional calculations
  • Infrared intensities
  • Radical ions
  • Vibrational analyses

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Density functional study on the structures and vibrational spectra of the radical anion and cation of biphenyl. / Furuya, Kazuhiko; Torii, Hajime; Furukawa, Yukio; Tasumi, Mitsuo.

In: Journal of Molecular Structure: THEOCHEM, Vol. 424, No. 3, 18.02.1998, p. 225-235.

Research output: Contribution to journalArticle

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