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Electronic structure, Non-linear properties and Vibrational analysis of ortho, meta and para -Hydroxybenzaldehyde by Density Functional Theory

Author Affiliations

  • 1 Physics Department, University of Lucknow, Lucknow, INDIA

Res. J. Recent Sci., Volume 2, Issue (ISC-2012), Pages 150-157, February,2 (2013)

Abstract

The present communication is aimed at comparing the molecular structural properties, vibrational and energetic data of ortho, meta and para hydroxybenzaldehyde, in gas phase, due to their commercial importance. The ground state properties of the title molecules have been calculated employing DFT/ B3LYP level of theory using the 6-311++G(d,p) basis set. The mean polarizability of all the three isomers are found to be nearly same in the range 88.415 to 90.933/a.u., but the dipole moment for ortho and meta hydroxybenzaldehyde are calculated to be 5.0201 and 4.9101 Debye whereas the dipole moment for para hydroxybenzaldehyde has slightly lower value at 3.4655 Debye. The first static hyperpolarizability of 'p'- hydroxybenzaldehyde is found to be 1.5 times higher to that of 'm'-hydroxybenzaldehyde and 5 times higher than 'o'- hydroxybenzaldehyde. MESP surfaces have also been drawn and compared. In order to obtain a complete description of molecular dynamics, vibrational wavenumber calculation along with the normal mode analysis, have been carried out at the DFT level. The calculated spectra of the molecules agree well with the experimental data.

References

  1. Andersen A, Final report on the safety assessment of benzaldehyde, Int J. Toxicol, (25 Suppl 1), 11-27, (2006) , 150-157 (2013)
  2. Liu Y., Sakagami H., Hashimoto K., Kikuchi H., Amano O.,Ishihara M., Kanda Y., Kunni S., Kochi M., Zhang W., Yu G., Tumor-specific Cytotoxicity and Type of Cell Death Induced by‚ -Cyclodextrin Benzaldehyde Inclusion Compound, Anticancer Research, (28), 229-236 (2008)
  3. Takeuchi S., Kochi M., Sakaguchi K., Nakagawa K. and Mizutani T., Benzaldehyde as a Carcinostatic Principle in Figs, Agric Biol Chem, (42) 1449-1451 (1978)
  4. Haraguchi S.K., Silva A.A., Vidotti G.J., Santos P.V. and Garcia F.P., Antitrypanosomal Activity of Novel Benzaldehyde-Thiosemicarbazone Derivatives from Kaurenoic Acid, Molecules, (16) 1166-1180 (2011)
  5. Itoh T., Akai N. and Ohno K., Journal of Molecular Structure, (786), 39-45 (2006)
  6. Strand T.G., Tafipolsky M.A., Vilkov L.V. and Volden H.V., The molecular structure of ortho- and meta-fluorobenzaldehyde by joint analysis of gas electron diffraction, microwave spectroscopy and ab initio molecular orbital calculations, Journal of Molecular Structure, (443), 9-16 (1998)
  7. Bock E. and Tomchuk E., Electric Moments and Conformations of ortho-, meta-, and para-Fluorobenzaldehyde, Canadian Journal of Chemistry, (50) 2890- 2891 (1972)
  8. Anderson P.D.J., Fernandez M.T., Pocsfalvi G. and Mason R.S., Thermodynamics of gas phase proton transfer reactions involvingsubstituted Benzaldehydes, J.Chem.Soc., Perkin Trans, 2(5), 873-880 (1997)
  9. Anjaneyulu A. and Rao G.R., Vibrational analysis of substituted benzaldehydes: Part I. Vibrational spectra, normal co-ordinate analysis and transferability of force constants of monohalogenated benzaldehydes Spectrochim. Acta Part A, (55), 749-760 (1999)
  10. http://webbook.nist.gov/chemistry/form-ser.html (2012)
  11. Kohn W. and Sham L.J., Self-consistent equations including exchange and correlation effects, Phys. Rev., (140) 1133–1138 (1965)
  12. Becke A.D., Density functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., (98) 648– 5652 (1993)
  13. Lee C., Yang W., Parr R.G., Development of the Colle Salvetti correlation- energy formula into a functional of the electron density, Phys. Rev., (37), 785–789 (1998)
  14. Miehlich B., Savin A., Stoll A. and Preuss H., Results obtained with the correlation energy density functional of Becke and Lee, Yang and Parr, Chem. Phys. Lett., (157), 200–206 (1989)
  15. Frisch M.J. et. al. Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford CT (2009)
  16. Scott A.P. and Random L., Harmonic vibrational frequencies: An evaluation of Hartree–Fock, Mller– Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors, J. Phys.Chem.- US, (100), 16502-16513 (1996)
  17. Denington II, Roy, Keith T., Millam J., Eppinnett K. Hovell W.L. and Gilliland, R., Gauss View, Version 3.07 Semichem, Inc., Shawnee Mission, KS (2003)
  18. Jamroz M.H., Vibrational Energy Distribution Analysis: VEDA 4 program, Warsaw (2004)
  19. Kleinman D.A., Nonlinear dielectric polarization in optical media, Phys. Rev. (126) 1977–1979 (1962)
  20. Pipek J. and Mezey P.Z., A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions, J. Chem. Phys, (90) 4916–4926 (1989)
  21. Buckingham A.D., Permanent and induced molecular moments and long-range intermolecular forces, Adv. Chem. Phys, (12) 107–142 (1967)
  22. Kanis D.R., Ratner M.A. and Marks T.J., Design and Construction of Molecular Assemblies with Large Second-Order Optical Nonlinearities. Quantum Chemical Aspects, Chem. Rev., (94), 195- 242 (1994)
  23. Sykes P., A Guidebook to Mechanism In Organic Chemistry. pp 15, Sixth Edition, Longman Publishing Group (1986)
  24. Fleming I., Frontier Orbitals and Organic Chemical Reactions (John Wiley and Sons, New York (1976)
  25. Murray J.S. and Sen K., Molecular Electrostatic Potentials, Concepts and Applications, Elsevier, Amsterdam (1996)
  26. Alkorta I. and Perez J.J., Molecular polarization potential maps of the nucleic acid bases, Int. J. Quant. Chem., (57) 123–135 (1996)
  27. Scrocco E. and Tomasi J., Advances in Quantum Chemistry, ( 2), P. Lowdin, ed., Academic Press, New York (1978)
  28. Luque F.J., Orozco M., Bhadane P.K. and Gadre S.R., SCRF calculation of the effect of water on the topology of the molecular electrostatic potential, J. Phys. Chem., ( 97) 9380–9384 (1993)
  29. Sponer J. and Hobza P., DNA base amino groups and their role in molecular interactions: Ab initio and preliminary density functional theory calculations, Int. J. Quant. Chem, (57) 959–970 (1996)
  30. Scott A.P. and Random L., Harmonic vibrational frequencies: An evaluation of Hartree–Fock, Mller–Plesset, quadratic configuration interaction, density functional theory and semiempirical scale factors, J. Phys. Chem., (100), 16502–16513 (1996)
  31. Pulay P., Fogarasi G., Pongor G., Boggs J.E. and Vargha A., Combination of theoretical ab initio and experimental information to obtain reliable harmonic force constants. Scaled quantum mechanical (QM) force fields for glyoxal, acrolein, butadiene, formaldehyde, and ethylene, J. Am. Chem. Soc., (105), 7037–7047 (1983)