DOI: 10.1063/1.477928. Torsional potential of biphenyl: <i>Ab initio</i> calculations with the Dunning correlation consisted basis sets

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

10.1063/1.477928

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

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 Mo/ller-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.

Bibliography

Tsuzuki, S., Uchimaru, T., Matsumura, K., Mikami, M., & Tanabe, K. (1999). Torsional potential of biphenyl: Ab initio calculations with the Dunning correlation consisted basis sets. The Journal of Chemical Physics, 110(6), 2858â2861.

Authors 5

Seiji Tsuzuki (first)
Tadafumi Uchimaru (additional)
Kazunari Matsumura (additional)
Masuhiro Mikami (additional)
Kazutoshi Tanabe (additional)

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:17 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 7:53 p.m.)
Indexed	1 month ago (Aug. 6, 2025, 8:22 a.m.)
Issued	26 years, 6 months ago (Feb. 8, 1999)
Published	26 years, 6 months ago (Feb. 8, 1999)
Published Print	26 years, 6 months ago (Feb. 8, 1999)

Funders 0

None

BibTeX

@article{Tsuzuki_1999, title={Torsional potential of biphenyl: Ab initio calculations with the Dunning correlation consisted basis sets}, volume={110}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.477928}, DOI={10.1063/1.477928}, number={6}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Tsuzuki, Seiji and Uchimaru, Tadafumi and Matsumura, Kazunari and Mikami, Masuhiro and Tanabe, Kazutoshi}, year={1999}, month=feb, pages={2858–2861} }

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  "abstract": "<jats:p>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 Mo/ller-Plesset method (MP2). Although previous Hartree\u2013Fock (HF) and MP2 calculations showed that the internal rotational barrier height at 0\u00b0 (\u0394E0) was substantially larger than that at 90\u00b0 (\u0394E90), our MP2/cc-pVQZ//MP2/6-31G* calculations showed that \u0394E0 (2.28 kcal/mol) was close to \u0394E90 (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 \u0394E0 in the previous calculations.</jats:p>",
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