Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations
Using the methods of IR-spectroscopy and quantum chemical calculations, we determined the formation of an H-bond between the 1,2,3-benzotriazole molecule and the molecules of acetone, dioxane, DMF, and DMSO. Quantum chemistry methods have been used to calculate the sums of charge changes in the atom...
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Elsevier
2023-04-01
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| Series: | Journal of King Saud University: Science |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S101836472200711X |
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| author | M.Kh. Khodiev U.A. Holikulov Noureddine ISSAOUI Omar M. Al-Dossary Leda G. Bousiakoug N.L. Lavrik |
| author_facet | M.Kh. Khodiev U.A. Holikulov Noureddine ISSAOUI Omar M. Al-Dossary Leda G. Bousiakoug N.L. Lavrik |
| author_sort | M.Kh. Khodiev |
| collection | DOAJ |
| description | Using the methods of IR-spectroscopy and quantum chemical calculations, we determined the formation of an H-bond between the 1,2,3-benzotriazole molecule and the molecules of acetone, dioxane, DMF, and DMSO. Quantum chemistry methods have been used to calculate the sums of charge changes in the atoms of the 1,2,3-benzotriazole molecule and of proton acceptor molecules (acetone, dioxane, DMF, and DMSO) due to the formation of their complexes with an H-bond (H-complexes NH…O). The sum of charge changes was taken as a contribution of a covalent component to H-bond formation. It has been established that as the sum of charge changes in N, H, and O or H and O, forming the H-complex, increases, the enthalpy of H-complex formation (EF) decreases. On the contrary, the EO of H-complexes increases when the product of the initial charges on the H and O atoms increases. In the absence of H-complexes, the product of charges was considered the electrostatic component of H-bond formation. The criterion of the value of H-bond EF was the value of a low-frequency shift of the initial position of the maximum IR absorption band of the NH vibration of the 1,2,3-benzotriazole molecule relative to its position in a neutral CCl4 solvent. The results of QTAIM, NCI, and RDG analyses showed that the values of energy densities in BCPs have a positive value in the complexes formed by 1,2,3-benzotriazole with acetone, dioxane, and DMFA, and such hydrogen bonds are electrostatic in nature. In the complex formed by 1,2,3-benzotriazole and DMSO, it has a negative value and a covalent character. The data obtained have allowed for two main conclusions: (i) In the formation of the H-complexes of the 1,2,3-benzotriazole molecule with proton-acceptor molecules containing oxygen atoms, the main contribution to H-bond formation is made by the electrostatic component. (ii) The contribution of the covalent component increases with increasing enthalpy of H-bond formation. |
| first_indexed | 2024-04-11T00:42:24Z |
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| institution | Directory Open Access Journal |
| issn | 1018-3647 |
| language | English |
| last_indexed | 2024-04-11T00:42:24Z |
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| spelling | doaj.art-4cc642fadbbd41f58868654561b3a9632023-01-06T04:16:44ZengElsevierJournal of King Saud University: Science1018-36472023-04-01353102530Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculationsM.Kh. Khodiev0U.A. Holikulov1Noureddine ISSAOUI2Omar M. Al-Dossary3Leda G. Bousiakoug4N.L. Lavrik5Tajik National University, Dushanbe, TajikistanDepartment of Optics and Spectroscopy, Sharof Rashidov Samarkand State University, Samarkand, UzbekistanUniversity of Monastir, Faculty of Sciences, Laboratory of Quantum and Statistical Physics (LR18ES18), Monastir 5079, Tunisia; Corresponding author.Department of Physics and Astronomy, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia; Corresponding author.IMD Laboratories Co, R&D Section, Lefkippos Technology Park, NCSR Demokritos, PO Box 60037, 15130 Athens, GreeceV.V.Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of Russian Academy of Science, Novosibirsk, Russian FederationUsing the methods of IR-spectroscopy and quantum chemical calculations, we determined the formation of an H-bond between the 1,2,3-benzotriazole molecule and the molecules of acetone, dioxane, DMF, and DMSO. Quantum chemistry methods have been used to calculate the sums of charge changes in the atoms of the 1,2,3-benzotriazole molecule and of proton acceptor molecules (acetone, dioxane, DMF, and DMSO) due to the formation of their complexes with an H-bond (H-complexes NH…O). The sum of charge changes was taken as a contribution of a covalent component to H-bond formation. It has been established that as the sum of charge changes in N, H, and O or H and O, forming the H-complex, increases, the enthalpy of H-complex formation (EF) decreases. On the contrary, the EO of H-complexes increases when the product of the initial charges on the H and O atoms increases. In the absence of H-complexes, the product of charges was considered the electrostatic component of H-bond formation. The criterion of the value of H-bond EF was the value of a low-frequency shift of the initial position of the maximum IR absorption band of the NH vibration of the 1,2,3-benzotriazole molecule relative to its position in a neutral CCl4 solvent. The results of QTAIM, NCI, and RDG analyses showed that the values of energy densities in BCPs have a positive value in the complexes formed by 1,2,3-benzotriazole with acetone, dioxane, and DMFA, and such hydrogen bonds are electrostatic in nature. In the complex formed by 1,2,3-benzotriazole and DMSO, it has a negative value and a covalent character. The data obtained have allowed for two main conclusions: (i) In the formation of the H-complexes of the 1,2,3-benzotriazole molecule with proton-acceptor molecules containing oxygen atoms, the main contribution to H-bond formation is made by the electrostatic component. (ii) The contribution of the covalent component increases with increasing enthalpy of H-bond formation.http://www.sciencedirect.com/science/article/pii/S101836472200711XH-bond1,2,3 – benzotriazoleDFTAIMELFNCI |
| spellingShingle | M.Kh. Khodiev U.A. Holikulov Noureddine ISSAOUI Omar M. Al-Dossary Leda G. Bousiakoug N.L. Lavrik Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations Journal of King Saud University: Science H-bond 1,2,3 – benzotriazole DFT AIM ELF NCI |
| title | Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations |
| title_full | Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations |
| title_fullStr | Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations |
| title_full_unstemmed | Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations |
| title_short | Estimation of electrostatic and covalent contributions to the enthalpy of H-bond formation in H-complexes of 1,2,3-benzotriazole with proton-acceptor molecules by IR spectroscopy and DFT calculations |
| title_sort | estimation of electrostatic and covalent contributions to the enthalpy of h bond formation in h complexes of 1 2 3 benzotriazole with proton acceptor molecules by ir spectroscopy and dft calculations |
| topic | H-bond 1,2,3 – benzotriazole DFT AIM ELF NCI |
| url | http://www.sciencedirect.com/science/article/pii/S101836472200711X |
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