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 journalArticlepeer-review

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
DOIs
Publication statusPublished - 1998 Feb 18
Externally publishedYes

Keywords

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

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Density functional study on the structures and vibrational spectra of the radical anion and cation of biphenyl'. Together they form a unique fingerprint.

Cite this