Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds
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...
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2016-06-01
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doaj-a041e99390bd4b7e87b9b171d175e7462020-11-24T22:21:04ZengCroatian Chemical SocietyCroatica Chemica Acta0011-16431334-417X2016-06-01891313510.5562/cca2681151120Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso CompoundsMarko Tomin0Igor Rončević1Zlatko Mihalić2Ruđer Bošković Institute, Bijenička cesta 54, HR-10000 Zagreb, CroatiaFaculty of Science, University of Zagreb, Horvatovac 102A, HR-10000 Zagreb, CroatiaFaculty of Science, University of Zagreb, Horvatovac 102A, HR-10000 Zagreb, CroatiaThe 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. <br><a rel="license" href="http://creativecommons.org/licenses/by/4.0/"><img alt="Creative Commons License" style="border-width:0" src="https://i.creativecommons.org/l/by/4.0/80x15.png" /></a> This work is licensed under a <a rel="license" href="http://creativecommons.org/licenses/by/4.0/">Creative Commons Attribution 4.0 International License</a>.http://hrcak.srce.hr/file/222315 |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Marko Tomin Igor Rončević Zlatko Mihalić |
spellingShingle |
Marko Tomin Igor Rončević Zlatko Mihalić Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds Croatica Chemica Acta |
author_facet |
Marko Tomin Igor Rončević Zlatko Mihalić |
author_sort |
Marko Tomin |
title |
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds |
title_short |
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds |
title_full |
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds |
title_fullStr |
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds |
title_full_unstemmed |
Comparison of DFT Methods for the Investigation of the Reduction Mechanisms of Aromatic Nitro- and Nitroso Compounds |
title_sort |
comparison of dft methods for the investigation of the reduction mechanisms of aromatic nitro- and nitroso compounds |
publisher |
Croatian Chemical Society |
series |
Croatica Chemica Acta |
issn |
0011-1643 1334-417X |
publishDate |
2016-06-01 |
description |
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.
<br><a rel="license" href="http://creativecommons.org/licenses/by/4.0/"><img alt="Creative Commons License" style="border-width:0" src="https://i.creativecommons.org/l/by/4.0/80x15.png" /></a> This work is licensed under a <a rel="license" href="http://creativecommons.org/licenses/by/4.0/">Creative Commons Attribution 4.0 International License</a>. |
url |
http://hrcak.srce.hr/file/222315 |
work_keys_str_mv |
AT markotomin comparisonofdftmethodsfortheinvestigationofthereductionmechanismsofaromaticnitroandnitrosocompounds AT igorroncevic comparisonofdftmethodsfortheinvestigationofthereductionmechanismsofaromaticnitroandnitrosocompounds AT zlatkomihalic comparisonofdftmethodsfortheinvestigationofthereductionmechanismsofaromaticnitroandnitrosocompounds |
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1725772403029573632 |