Analysis of the Chemical Reactivity of Limonene by the Functional Density Theory Method Using Global Descriptors

Subject Areas : Journal of Chemical Health Risks

Hayat  EL Ouafy ¹ (Team of Analytical & Computational Chemistry, Nanotechnology and Environment, Department of Chemistry and Environment, Faculty of Science and Technics, Sultan Moulay Slimane University, Beni Mellal, Morocco)
Tarik  EL Ouafy ² (Team of Analytical & Computational Chemistry, Nanotechnology and Environment, Department of Physics and Chemistry, Polydisciplinary Faculty of Khouribga, Sultan Moulay Slimane University, Beni Mellal, Morocco)
Mustapha  Oubenali ³ (Team of Analytical & Computational Chemistry, Nanotechnology and Environment, Department of Chemistry and Environment, Faculty of Science and Technics, Sultan Moulay Slimane University, Beni Mellal, Morocco)
Aziz  EL Haimouti ⁴ (Team of Analytical & Computational Chemistry, Nanotechnology and Environment, Department of Physics and Chemistry, Polydisciplinary Faculty of Khouribga, Sultan Moulay Slimane University, Beni Mellal, Morocco)
Ahmed  Gamouh ⁵ (Team of Analytical & Computational Chemistry, Nanotechnology and Environment, Department of Chemistry and Environment, Faculty of Science and Technics, Sultan Moulay Slimane University, Beni Mellal, Morocco)
Mohamed  Mbarki ⁶ (Laboratory of Organic and Analytical Chemistry, Sultan Moulay Slimane University, Faculty of Science and Technology, Beni Mellal, Morocco)

Received: 2020-09-22 Accepted : 2021-03-24 Published : 2021-06-01

Keywords: DFT, HOMO, LUMO, (R)-Limonene, (S)-Limonene, Chemical descriptors, NLO, Electrostatic molecular potential,

Abstract :

The optimized molecular geometry is interpreted using structural optimizations based on the Functional Density Theory (DFT) method. Additionally, we used B3LYP / 6-311G (d, p) to determine the chemical descriptor, the ionization potential (I), the electron affinity (A), the chemical potential (μ), the chemical hardness (η), 3D maps of HOMO and LUMO orbits were used to develop the structure, activity, and structure of quantitative relationships. Large basis set-theoretical calculations of the dipole polarizabilities and second hyperpolarizabilities of limonene molecules have been carried out and the results have been used to assess optical properties of atomic contributions to the overall molecular response tensors. Reasonable estimates of the mean second hyperpolarizability response can be obtained from summing atomic parameters obtained here, though the reliability of the estimates is worse than what is found for dipole polarizabilities. The DFT method has been used of which is to compare the angles and lengths of molecular bonds with the experimental results. To understand molecular interactions in a given molecule, electrostatic molecular potential (MEP) is a crucial tool. Also, the sites of relative reactivity for electrophilic and nucleophilic attacks. Theoretical studies of the molecules of (R)-limonene and (S)-limonene made it possible to confirm the results obtained experimentally.

References:

1. Batista S.A.A., Vandresen F., Falzirolli H., Britta E., Oliveira D.N., Catharino R.R., Silva C.C., 2019. Synthesis and comparison of antileishmanial and cytotoxic activities of S-(−)-limonene benzaldehyde thiosemicarbazones with their R-(+)-analogues. J Mol Stru. 1179(11), 252-262.


2. Shen H., Wu G., Wang P., 2014. Intra-molecular enantiomerism in R-(+)-Limonene as evidenced by the differentialbondpolarizabilities. Spectr Acta Part A: Mol Biom Spectr. 128(7), 838-843.


3. Yarovaya O.I., Korchagina D.V., Salomatina O.V. Polovinka, M.P., Barkhash V.A., 2003. Synthesis of heterocyclic compounds in acid-catalised reactions of citral epoxides. Mend Commun. 13(1), 27-29.


4. Lakbaibi Z., Abou El Makarim H., Tabyaoui M., El Hajbi A., 2014. A theoretical study by the quantum method DFT B3LYP / 6-311G (d, p) of the reaction of formation of α-chlorinated glycidic esters in aliphatic series [Theoretical study of the formation of α-chloroglycidic esters in aliphatic series by the quantum method DFT with B3LYP / 6-311G (d, p)]. Inter J Innov Appl Stud. 7(2), 602-616.


5. Rossi-Fernández A.C., Meier L.A., Castellani N.J., 2019. Neutral and zwitterionic dopamine species adsorbed on silver surfaces: A DFT investigation of interaction mechanism. J Inter Chem Quant. 119(5), 1-18.


6. Thanikaivelan P., Subramanian V., Raghava Rao J., Unni Nair B., 2000. Application of quantum chemical descriptor in quantitative structure activity and structure property relationship. Chem Phys Lett. 323(1-2), 59-70.


7. Suresh S., Gunasekaran S., Srinivasan S., 2014. Spectroscopic (FT-IR, FT-Raman, NMR and UV-Visible) and quantum chemical studies of molecular geometry, Frontier molecular orbital, NLO, NBO and thermodynamic properties of salicylic acid. Spectro Acta Part A: Mol Biom Spectr. 132(6),130-141.


8. Dobado J.A., Molina J., 1999. Adenine-Hydrogen Peroxide System: DFT and MP2 Investigation. J Phys Chem A. 103(24), 4755-4761.


9. Kavitha E., Sundaraganesan N., Sebastian S., Kurt M., 2010. Molecular structure, anharmonic vibrational frequencies and NBO analysis of naphthalene acetic acid by density functional theory calculations. Spectro Acta Part A: Mol Biom Spectr. 77(3), 612-619.


10.  


11.  Sebastian S., Sylvestre S., Jayabharathi J., Ayyapand S., Amalanathan M., Oudayakumar K., 2005.  Study on conformational stability, molecular structure, vibrational spectra, NBO, TD-DFT, HOMO and LUMO analysis of 3,5-dinitrosalicylic acid by DFT techniques. Spectro Acta Part A: Mol Biom Spectr. 136(2), 1107-1118.

 12. Liu L., Gao H., 2012. Molecular structure and vibrational spectra of ibuprofen using density function theory calculations. Spectro Acta Part A : Mol Biom Spectr. 89(4), 201-209.

13.Cankaya N., Tanış E., Gülbaş H.E., Bulut N., 2019. Une nouvelle synthèse de copolymère de limonène: analyse expérimentale et théorique. Poly Bull. 76(3), 3297-3327.

14.Han J., Lee H., Tao F.M., 2005. Molecular structures and properties of the complete series of bromophenols: Density functional theory calculations. J Phys Chem A. 109(23), 5186-5192.

15.Maps T.F., 1994. Representation of molecular electrostatic potentials by topological feature maps. J Amer Chem Soci. 116(11), 4608-4620.