Skip to main content
SpringerLink
Log in

Gradient optimization of polarization exponents inab initio MO calculations on H2SO → HSOH and CH3SH → CH2SH2

  • Published:
Theoretica chimica acta Aims and scope Submit manuscript

Summary

Analytical gradients were used to optimize the polarization function exponents in the 6-31G(d) and 6-31G(d, p) basis sets for the reactants, transition structures and products in the reactions H2SO → HSOH and CH3SH → CH2SH2. The optimizedd exponents on the heavy atoms change by ±10% in the course of the reactions and depend on the bonding of the heavy atoms. Thep exponents on the hydrogens change by as much as a factor of 5 and depend on the element to which the hydrogen is bonded and its valency. The effect of exponent optimization on the relative energies is small (±3 kcal/mol). With the 6-31G(d, p) basis set, optimization of the polarization exponents can make some of the bonds significantly more polar, as judged by the Mulliken charges.

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. Davidson ER, Feller D (1986) Chem Rev 86:681

    Google Scholar 

  2. Huzinaga S (1985) Comp Phys Rep 2:279

    Google Scholar 

  3. Hehre WJ, Ditchfield R, Pople JA (1972) J Chem Phys 56:2257; Francl MM, Pietro WJ, Hehre WJ, Binkley JS, Gordon MS, DeFrees DJ, Pople JA (1982) J Chem Phys 77:3654; Hariharan PC, Pople JA (1973) Theor Chim Acta 28:213

    Google Scholar 

  4. Dehn JT (1962) J Chem Phys 11:2549

    Google Scholar 

  5. Moccia R (1967) Theor Chim Acta 8:8

    Google Scholar 

  6. Kari R, Sutcliffe BT (1970) Chem Phys Lett 7:149

    Google Scholar 

  7. Faegri Jr K, Almlöf J (1986) J Comp Chem 7:396

    Google Scholar 

  8. Roos B, Siegbahn P (1970) Theor Chim Acta 17:199

    Google Scholar 

  9. Goddard JD, Csizmadia IG, Mezey PG, Kari RE (1977) J Chem Phys 66:3545; Poirier RA, Daudel R, Csizmadia IG (1980) Int J Quantum Chem 18:715, 727; (1981) ibid 19:711; Daudel R, Poirier RA, Csizmadia IG (1982) Int J Quantum Chem 21:699

    Google Scholar 

  10. Mezey PG, Haas E-C (1982) J Chem Phys 77:870; (1983) J Comp Chem 4:482

    Google Scholar 

  11. Hashimoto K, Osamura Y (1989) Chem Phys Lett 164:353

    Google Scholar 

  12. Wolfe S, Schlegel HB, Gazz Chim Ital in press, and references therein

  13. Mitchell DJ, Wolfe S, Schlegel HB (1981) Can J Chem 59:3280; Eades RA, Gassman PG, Dixon DA (1981) J Am Chem Soc 103:1066; Dixon DA, Dunning Jr TH, Eades RA, Gassman PG (1983) J Am Chem Soc 105:7011

    Google Scholar 

  14. Schlegel HB (1982) J Chem Phys 77:3676; Tonachini G, Schlegel HB (1987) J Chem Phys 87:514

    Google Scholar 

  15. Frisch MJ, Head-Gordon M, Schlegel HB, Raghavachari K, Binkley JS, Gonzalez C, DeFrees D, Fox DJ, Whiteside RA, Seeger R, Melius CF, Baker J, Martin R, Kahn LR, Stewart JJP, Fluder EM, Topiol S, Pople JA (1988) GAUSSIAN 88, Gaussian, Inc, Pittsburgh, PA

    Google Scholar 

  16. Broyden CG (1970) J Inst Math Appl 6:76; Fletcher R (1970) Comput J 13:317; Goldfarb D (1970) Math Comput 24:23; Shanno DF (1970) ibid 24:647

    Google Scholar 

  17. Fletcher R (1980) Practical methods of optimization. Wiley, New York

    Google Scholar 

Download references

Author information

Author notes

  1. Miquel Solà

    Present address: Department de Química, Universitat Autònoma de Barcelona, E-08193, Bellaterra, Spain

  2. Glauco Tonachini

    Present address: Istituto di Chimica Organica, Universitá di Torino, I-10125, Torino, Italy

Authors and Affiliations

  1. Department of Chemistry, Wayne State University, 48202, Detroit, USA

    Miquel Solà, Carlos Gonzalez, Glauco Tonachini & H. Bernhard Schlegel

  2. Camile and Henry Dreyfus Scholar, USA

    H. Bernhard Schlegel

Authors
  1. Miquel Solà
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Carlos Gonzalez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Glauco Tonachini
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. H. Bernhard Schlegel
    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

Solà, M., Gonzalez, C., Tonachini, G. et al. Gradient optimization of polarization exponents inab initio MO calculations on H2SO → HSOH and CH3SH → CH2SH2 . Theoret. Chim. Acta 77, 281–287 (1990). https://doi.org/10.1007/BF01116551

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01116551

Key words

Search

Navigation