### 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° (ΔE_{0}) was substantially larger than that at 90° (ΔE_{90}), our MP2/cc-pVQZ//MP2/6-31G* calculations showed that ΔE_{0} (2.28 kcal/mol) was close to ΔE_{90} (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 ΔE_{0} in the previous calculations.

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

Pages (from-to) | 2858-2861 |

Number of pages | 4 |

Journal | Journal of Chemical Physics |

Volume | 110 |

Issue number | 2-12 |

Publication status | Published - 1999 Feb 8 |

Externally published | Yes |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*Journal of Chemical Physics*,

*110*(2-12), 2858-2861.

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

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 110, no. 2-12, pp. 2858-2861.

}

TY - JOUR

T1 - Torsional potential of biphenyl

T2 - Ab initio calculations with the Dunning correlation consisted basis sets

AU - Tsuzuki, Seiji

AU - Uchimaru, Tadafumi

AU - Matsumura, Kazunari

AU - Mikami, Masuhiro

AU - Tanabe, Kazutoshi

PY - 1999/2/8

Y1 - 1999/2/8

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0001066725&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0001066725&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0001066725

VL - 110

SP - 2858

EP - 2861

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 2-12

ER -