Croatica Chemica Acta, Vol. 89 No. 1, 2016.
Preliminary communication
https://doi.org/10.5562/cca2681
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds
Marko Tomin
; Ruđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, Croatia
Igor Rončević
; Faculty of Science, University of Zagreb, Horvatovac 102A, HR-10000 Zagreb, Croatia
Zlatko Mihalić
; Faculty of Science, University of Zagreb, Horvatovac 102A, HR-10000 Zagreb, Croatia
Abstract
The main goal of this paper is to find an adequate level of theory for the computational investigation of the reduction mechanisms of aromatic nitro- and nitroso compounds. To this end, five standard reduction potentials of nitro- and nitrosobenzene in three different solvents and four pKa values of species involved in the mechanism were compared with the values calculated at different DFT and CBS-X levels of theory. Out of fourteen tested functionals, five showed good linear correlation between calculated and experimental ΔrG° values. However, at all explored levels of theory, the calculated ΔrG° values systematically deviate from the experimental ones, indicating the necessity of better description of solvation effects for charged species, possibly via a cluster-continuum approach.
This work is licensed under a Creative Commons Attribution 4.0 International License.
Keywords
aromatic nitro compounds; reduction mechanism; DFT calculations; solvation
Hrčak ID:
151120
URI
Publication date:
20.6.2016.
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