Skip to main content
SpringerLink
Log in

The internal rotational barrier of biphenyl studied with multiconfigurational second-order perturbation theory (CASPT2)

  • Published:
Theoretica chimica acta Aims and scope Submit manuscript

Summary

A detailedab initio study of the molecular structure and rotational barriers of biphenyl has been performed. First, non-dynamical correlation effects involving the π system are taken into account at the CASSCF level. These wave functions are subsequently employed as reference functions in a multiconfigurational second-order perturbation treatment (CASPT2). The performance single-reference approaches is in addition analysed. The molecular geometries of biphenyl in twisted, coplanar, and perpendicular conformations have been optimized at the CASSCF level. A rotational angle of 44.3° is predicted for the minimum energy conformer in agreement with gas-phase electron diffraction data (44.4±1.2°). The highest level of theory employed yields the values 12.93 (6.0±2.1) and 6.40 (6.5±2.5) kJ/mol for the barrier heights at 0° and 90°, respectively (electron diffraction data within parentheses). In the light of the present findings, the reliability of the available experimental data is discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Rabolt JF, Clarke TC, Kanazawa KK, Reynolds JR, Street GB (1980) J Chem Soc Chem Commun 347; Chance RR, Shacklette LW, Miller GG, Ivori DM, Sowa JM, Elsenbaumer RL, Baughman RH (1980) J Chem Soc Chem Commun. 348; Brédas JL, Silbey R (eds) (1991) in: Conjugated polymers: the novel science and technology of highly conducting and nonlinear optically active materials; Kluwer, Dordrecht, the Netherlands

  2. Brédas JL, Street GB (1985) Acc Chem Res 18:309

    Google Scholar 

  3. Furukawa Y, Ohtsuka H, Tasumi M (1993) Synth Met 55–57:516

    Google Scholar 

  4. Ramsey MG, Steinmüller D, Netzer FP (1990) Phys Rev B42:5902

    Google Scholar 

  5. Meerholz K, Heinze J (1990) Angew Chem Int Ed Engl 29:692

    Google Scholar 

  6. Ramsey MG, Netzer FP, Steinmüller D, Steinmüller-Nethl D, Lyod DR (1992) J Chem Phys 97:4489

    Google Scholar 

  7. Kurland RJ, Wise WB (1964) J Am Chem Soc 86:1877

    Google Scholar 

  8. Carreira LA, Towns TG (1977) J Mol Struct 41:1

    Google Scholar 

  9. Almenningen A, Bastiansen O, Fernholt L, Cyvin BN, Cyvin SJ, Samdal S (1985) J Mol Struct 128:59.

    Google Scholar 

  10. Bastiansen O, Samdal S (1985) J Mol Struct 128:115

    Google Scholar 

  11. Akiyama M, Watanabe T, Kakihana M (1986) J Phys Chem 90:1752

    Google Scholar 

  12. Takei Y, Yamaguchi T, Osamura Y, Fuke K, Kaya K (1988) J Phys Chem 92:577

    Google Scholar 

  13. Im H, Bernstein ER (1988) J Chem Phys 88:7337

    Google Scholar 

  14. Almlöf J (1974) Chem Phys 6:135

    Google Scholar 

  15. McKinney JD, Gottschalk KE, Pedersen L (1983) J Mol Struct (THEOCHEM) 104:445

    Google Scholar 

  16. Penner GH (1986) J Mol Struct (THEOCHEM) 137:191

    Google Scholar 

  17. Häfelinger G, Regelmann C (1985) J Comput Chem 6:368

    Google Scholar 

  18. Häfelinger G, Regelmann C (1987) J Comput Chem 8:1057

    Google Scholar 

  19. Tsuzuki S, Tanabe K (1991) J Phys Chem 95:139

    Google Scholar 

  20. Cioslowski J, Mixon ST (1992) J Am Chem Soc 114:4382

    Google Scholar 

  21. Brédas JL, Street GB, Thémans B, André JM (1985) J Chem Phys 83:1323

    Google Scholar 

  22. Rao BK, Kestner NR, Darsey JA (1987) Z Phys D6:17

    Google Scholar 

  23. Kirin D (1988) J Phys Chem 92:3691

    Google Scholar 

  24. Almlöf J, Taylor PR (1987) J Chem Phys 86:4070

    Google Scholar 

  25. Widmark P-O, Malmqvist P-Å, Ross BO (1990) Theoret Chim Acta 77:291

    Google Scholar 

  26. Dunning TH, Hay PJ (1976) in: Modern theoretical chemistry, Plenum, New York, p 1

    Google Scholar 

  27. For a review of the CASSCF method see: Roos BO (1987) in: Lawley KP (ed) Ab initio methods in quantum chemistry II, Wiley, New York, p 399

    Google Scholar 

  28. Andersson K, Malmqvist P-Å, Roos BO, Sadlej AJ, Wolinski K (1990) J Phys Chem 94:5483

    Google Scholar 

  29. Andersson K, Malmqvist P-Å, Roos BO (1992) J Chem Phys 96:1218

    Google Scholar 

  30. Serrano-Andrés L, Lindh R, Roos BO, Merchán M (1993) J Phys Chem 97:9360; Serrano-Andrés L, Merchán M, Nebot-Gil I, Roos BO, Fülscher MP (1993) J Am Chem Soc 115:6184; Serrano-Andrés L, Merchán M, Fülscher MP, Roos BO (1993) Chem Phys Lett 211:125; González-Luque R, Merchán M, Borowski P, Roos BO (1993) Theoret Chim Acta 86:467; González-Luque R, Merchán M, Roos BO (1993) Chem Phys 171:107; Rubio M, Ortí E, Merchán M, Roos BO (1994) Chem Phys 179:395

    Google Scholar 

  31. Andersson K, Blomberg MRA, Fülscher MP, Kellö V, Lindh R, Malmqvist P-Å, Noga J, Olsen J, Roos BO, Sadlej AJ, Siegbahn PEM, Urban M, Widmark P-O (1991) MOLCAS, Version 2, University of Lund, Sweden

    Google Scholar 

  32. Lindh R, Ryu U, Liu B (1991) J Chem Phys 95:5889; Lindh R (1993) Theoret Chim Acta 85:423

    Google Scholar 

  33. MOLCAS-3 is an extension of the quantum chemistry package MOLCAS-2 (see Ref. [31]), University of Lund, Sweden, to be published

  34. Charbonneau G, Delugeard Y (1976) Acta Cryst B32:1420

    Google Scholar 

  35. Charbonneau G, Delugeard Y (1977) Acta Cryst B33:1586

    Google Scholar 

  36. Raghavachari K (1984) J Chem Phys 81:1383

    Google Scholar 

  37. Head-Gordon M, Pople JA (1993) J Phys Chem 97:1147

    Google Scholar 

  38. Baudour JL (1991) Acta Cryst B47:935

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Departament de Química Física, Universitat de Valéncia, Doctor Moliner 50, E-46100, Burjassot (Valéncia), Spain

    Mercedes Rubio, Manuela Merchán & Enrique Ortí

Authors
  1. Mercedes Rubio
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Manuela Merchán
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Enrique Ortí
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rubio, M., Merchán, M. & Ortí, E. The internal rotational barrier of biphenyl studied with multiconfigurational second-order perturbation theory (CASPT2). Theoret. Chim. Acta 91, 17–29 (1995). https://doi.org/10.1007/BF01113859

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01113859

Key words

Search

Navigation