Torsional potential of biphenyl: Ab initio calculations with the Dunning correlation consisted basis sets

Seiji Tsuzuki, Tadafumi Uchimaru, Kazunari Matsumura, Masuhiro Mikami, Kazutoshi Tanabe

Research output: Contribution to journalArticle

104 Citations (Scopus)

Abstract

The internal rotational barrier heights of biphenyl were calculated with the Dunning correlation consisted basis sets (up to cc-pVQZ, 960 basis functions) and the electron correlation correction by the second order Møller-Plesset method (MP2). Although previous Hartree-Fock (HF) and MP2 calculations showed that the internal rotational barrier height at 0° (ΔE0) was substantially larger than that at 90° (ΔE90), our MP2/cc-pVQZ//MP2/6-31G* calculations showed that ΔE0 (2.28 kcal/mol) was close to ΔE90 (2.13 kcal/mol), which agreed with the estimation from experimental measurements. The calculations of benzene dimers suggested that the dispersion interaction increased the relative stability of the coplanar conformer. The basis sets employed in the previous calculations were not large enough to evaluate the attractive dispersion interaction. The underestimation of the stabilization of the coplanar conformer by the dispersion interaction would be one of the reasons for the overestimation of ΔE0 in the previous calculations.

Original languageEnglish
Pages (from-to)2858-2861
Number of pages4
JournalJournal of Chemical Physics
Volume110
Issue number2-12
Publication statusPublished - 1999 Feb 8
Externally publishedYes

Fingerprint

Electron correlations
interactions
Benzene
Dimers
Stabilization
stabilization
benzene
dimers
diphenyl
electrons

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Torsional potential of biphenyl : Ab initio calculations with the Dunning correlation consisted basis sets. / Tsuzuki, Seiji; Uchimaru, Tadafumi; Matsumura, Kazunari; Mikami, Masuhiro; Tanabe, Kazutoshi.

In: Journal of Chemical Physics, Vol. 110, No. 2-12, 08.02.1999, p. 2858-2861.

Research output: Contribution to journalArticle

Tsuzuki, Seiji ; Uchimaru, Tadafumi ; Matsumura, Kazunari ; Mikami, Masuhiro ; Tanabe, Kazutoshi. / Torsional potential of biphenyl : Ab initio calculations with the Dunning correlation consisted basis sets. In: Journal of Chemical Physics. 1999 ; Vol. 110, No. 2-12. pp. 2858-2861.
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