Theoretical study of ionization potentials of N-heterocyclic compounds

Liudmyla K. Sviatenko

Abstract


The ability to predict the redox properties is an important tool for study electron transfer processes occurring in the gas-phase (atmospheric chemistry) or in the condensed phase (electrochemistry, biochemistry). MPWB1K/6-31+G(d) and MPWB1K/tzvp theoretical models were found to provide reasonable accuracy of the prediction of ionization potentials for mono- and polycyclic azacompounds. The root mean square errors of the methods are 0.19 and 0.20, respectively. While the mean absolute deviation for both methods is the same and equals to 0.15 eV. These theoretical models were applied to predict ionization potentials for compounds not evaluated experimentally. Influence of substitutes and a number of nitrogen atoms on value of ionization potential was analyzed. Methyl-, and phenyl- groups, and fused benzo cycle decrease ionization potentials of N-heterocycles. Increase of amount of nitrogen atoms in five-membered cycles leads to significant enlargement of ionization potentials.

Keywords


azacyclic compounds, DFT, ionization potential

Full Text:

PDF

References


Zhan C.-G., Nichols J. A., Dixon D. A., J. Phys. Chem. A, 2003, vol. 107, no 20, p. 4184-4195.

Uchimiya M., Gorb L., Isayev O., Qasim M. M., Leszczynski J., Environ Pollut., 2010, vol. 158, no. 10, p. 3048-3053.

Namazian M., Coote M. L., J. Phys. Chem. A, 2007, vol. 111, no. 30, p. 7227-7132.

Rayne S., Forest K., J. Chem. Eng. Data., 2011, vol. 56, no. 2, p. 350-355.

Fu Y., Liu L., Yu H.-Z., Wang Y.-M., Guo Q.-X., J. Am. Chem. Soc., 2005, vol. 127, no. 19, 7227-7234.

Xu W., Gao A., J. Mol. Struct: THEOCHEM, 2005, vol. 732, no. 1-3, p. 63-70.

Kose M., Theor. Chem. Acc., 2011, vol. 128, no. 2, p. 157-164.

Sviatenko L., Isayev O., Gorb L., Hill F., Leszczynski J., J. Comput. Chem., 2011, vol. 32, no. 10, p. 2195-2203.

Sviatenko L. K., Gorb L., Hill F., Leszczynski J., J. Comput. Chem., 2013, vol. 34, no. 13, p. 1094-1100.

Shankar R., Senthilkumar K., Kolandaivel P., Int. J. Quantum Chem., 2009, vol. 109, no. 4, p. 764-771.

Frisch, M. J., Trucks, G. W., Schlegel, H. B. et al., Gaussian 09, Revision A.02, Gaussian, Inc.: Wallingford CT, 2009.

Zhao Y., Truhlar D. G., J. Phys. Chem. A, 2004, vol. 108, no. 33, p. 6908-6918.

NIST Chemistry WebBook. NIST Standard Reference Database, 2005, no. 69. Available at http://webbook.nist.gov/chemistry/.




DOI: http://dx.doi.org/10.15421/081410

Refbacks

  • There are currently no refbacks.




Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

______________________________________________________
BULLETIN OF DNIPROPETROVSK NATIONAL UNIVERSITY
eISSN: 2313-4984 | pISSN: 2306-871X
Contact:chem.dnu@gmail.com
The journal publishes research papers on terms: Creative Commons Attribution 4.0 International License
Founder: Oles Honchar Dnipropetrovsk National University