Skip to main content
SpringerLink
Log in

A theoretical determination of the electronic spectrum of formaldehyde

  • Published:
Theoretica chimica acta Aims and scope Submit manuscript

Summary

The electronically excited states of formaldehyde are examined by means of multiconfigurational second-order perturbation (CASPT2) theory with extended ANO-type basis sets. The calculations comprised five valence excited states plus all singlet 3s, 3p, and 3d members of the Rydberg series converging on the first ionization. The computed vertical excitation energies were found to be within 0.2 eV of the available experimental energies. Full geometry optimization has been performed for five valence excited states. Assuming a planar geometry, the “0-0” transition for the valence1A1(π → π*) state is calculated to appear near 7.9 eV, close to the (n y → 3p) region. This state is, however, not planar and the true adiabatic energy is 7.4 eV, which is 2.3 eV below the corresponding vertical transition.

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. Robinson GW, Digiorgio VE (1958) Can J Chem Soc, p 31

  2. Mentall JE, Gentieu EP, Krauss M, Neumann D (1971) J Chem Phys 55:5471

    Google Scholar 

  3. Weiss MJ, Kuyatt CE, Mielczarek S (1971) J Chem Phys 54:4147

    Google Scholar 

  4. Chutjian A (1974) J Chem Phys 61:4279

    Google Scholar 

  5. Moule DC, Walsh AD (1975) Chem Rev 75:67

    Google Scholar 

  6. Lessard CR, Moule DC (1977) J Chem Phys 66:3908

    Google Scholar 

  7. Taylor S, Wilden DG, Comer J (1982) Chem Phys 70:291

    Google Scholar 

  8. Clouthier DJ, Ramsay DA (1983) Ann Rev Phys Chem 34:31

    Google Scholar 

  9. Brint P, Connerade J-P, Mayhew C, Sommer K (1985) J Chem Soc Faraday Trans 2 81:1643

    Google Scholar 

  10. Robin MB, (1985) In: Higher excited states of polyatomic molecules, Vol. 3. Academic Press, New York

    Google Scholar 

  11. Suto M, Wang X, Lee LC (1986) J Chem Phys 85:4228

    Google Scholar 

  12. Walzl KN, Koerting CF, Kuppermann A (1987) J Chem Phys 87:3796

    Google Scholar 

  13. Whitten JL, Hackmeyer M (1969) J Chem Phys 51: 5584

    Google Scholar 

  14. Buenker RJ, Peyerimhoff SD (1970) J Chem Phys 53:1368

    Google Scholar 

  15. Peyerimhoff SD, Buenker RJ, Kammer WE, Hsu H (1971) Chem Phys Lett 8:129

    Google Scholar 

  16. Whitten JL (1972) J Chem Phys 56:5458

    Google Scholar 

  17. Langhoff SR, Elbert ST, Jackels CF, Davidson ER (1974) Chem Phys Lett 29:247

    Google Scholar 

  18. Harding LB, Goddard III WA (1975) J Am Chem Soc 97:6293

    Google Scholar 

  19. Harding LB, Goddard III WA (1977) J Am Chem Soc 99:677

    Google Scholar 

  20. Davidson ER, McMurchie LE (1982) In Excited states, Vol. 5. Academic Press, New York

    Google Scholar 

  21. Fitzgerald G, Schaefer III HF (1985) J Chem Phys 83:1162

    Google Scholar 

  22. Allen WD, Schaefer III HF (1987) J Chem Phys 87:7076

    Google Scholar 

  23. Galasso V (1990) J Chem Phys 92:2495

    Google Scholar 

  24. Foresman JB, Head-Gordon M, Pople JA, Frisch MJ (1992) J Phys Chem 96:135

    Google Scholar 

  25. Hadad CM, Foresman JB, Wiberg KB (1993) J Phys Chem 97:4293

    Google Scholar 

  26. Head-Gordon M, Rico RJ, Oumi M, Lee TJ (1994) Chem Phys Lett 219:21

    Google Scholar 

  27. Hachey M, Bruna PJ, Grein F (1994) J Chem Soc Faraday Trans 90:683

    Google Scholar 

  28. Hachey MRJ, Bruna PJ, Grein F (1995) J Phys Chem 99:8050

    Google Scholar 

  29. Niu B, Shirley DA, Bai Y (1993) J Chem Phys 98:4377

    Google Scholar 

  30. Serrano-Andrés L, Merchán M, Nebot-Gil I, Lindh R, Roos BO (1993) J Chem Phys 98:3151

    Google Scholar 

  31. Roos BO (1987) In: Lawley KP (ed) Advances in chemical physics; ab initio methods in quantum chemistry — II, Ch. 69, Wiley, Chichester, p 399

    Google Scholar 

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

    Google Scholar 

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

    Google Scholar 

  34. Andersson K, Roos BO (1994) In: Yarkony R (ed) Modern electron structure theory, Vol. 1. World Scientific Publishing, New York

    Google Scholar 

  35. Roos BO, Fülscher MP, Malmqvist Per-Åke, Merchán M, Serrano-Andrés L (1994) In: Langhoff SR (ed) Quantum mechanical electronic structure calculations with chemical accuracy. Kluwer, Dordrecht

    Google Scholar 

  36. McDiarmid R, private communication

  37. Widmark P-O, Malmqvist P-Å, Roos BO (1990) Theor Chim Acta 77:291

    Google Scholar 

  38. Fülscher MP, Lorentzon J, Malmqvist P-Å, Roos BO (to be published)

  39. Kaufmann K, Baumeister W, Jungen M (1989) J Phys B: At Mol Opt Phys 22:2223

    Google Scholar 

  40. Takagi K, Oka T (1963) J Phys Soc Jpn 18:1174

    Google Scholar 

  41. Andersson K, Roos BO (1993) Int J Quantum Chem 45:591

    Google Scholar 

  42. Malmqvist P-Å (1986) Int J Quantum Chem 30:479

    Google Scholar 

  43. Malmqvist P-Å, Roos BO (1989) Chem Phys Lett 155:189

    Google Scholar 

  44. 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 (1992) MOLCAS version 2 user's guide. Department of Theor Chem, Chem Center, University of Lund, Lund

    Google Scholar 

  45. Duncan JL (1974) Mol Phys 28:1177

    Google Scholar 

  46. Jensen P, Bunker PR (1982) J Mol Spectr 94:114

    Google Scholar 

  47. Bauschlicher CW, Shavitt I (1978) J Am Chem Soc 100:739

    Google Scholar 

  48. Merchán M, Roos BO, McDiarmid R (to be published)

Download references

Author information

Authors and Affiliations

  1. Departamento de Química Física, Universitat de València, Dr. Moliner 50, Burjassot, E-46100, Valencia, Spain

    Manuela Merchán

  2. Department of Theoretical Chemistry, Chemical Centre, P.O.B. 124, S-22100, Lund, Sweden

    Björn O. Roos

Authors
  1. Manuela Merchán
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Björn O. Roos
    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

Merchán, M., Roos, B.O. A theoretical determination of the electronic spectrum of formaldehyde. Theoret. Chim. Acta 92, 227–239 (1995). https://doi.org/10.1007/BF01125948

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01125948

Key words

Search

Navigation