Ab-initio Estimation of Solvation Effect, Thermodynamic and Spectroscopic analysis of Salicylic Acid
DOI:
https://doi.org/10.5281/zenodo.15252078Abstract
Salicylic acid (C7H6O3) is an important compound (phenolic) used in the manufacture of pharmaceuticals, textiles, and skin care products. It is also used as a preservative. In the present study, the Density functional theory (DFT) method was used with 6-311++G (d,p) basis set and B3LYP to investigate solvation effects of gas phase, benzene, chloroform, dichloro-methane, dimethyl-sulfoxide (DSMO), and water on salicylic acid. We also investigated the bond length, bond angle, frontier molecular orbital energies (FMOE), global quantities, nonlinear optical properties, and thermodynamic properties of Salicylic acid in these solvents. The analysis of the HOMO-LUMO band gap revealed an increasing trend with solvent polarity, with water exhibiting the highest stability at 4.7928 eV. Ionization potentials (IPs), electron affinities (EAs), and global chemical indices all exhibited a direct relationship with solvent polarity. In addition, we investigated the nonlinear optical properties such as dipole moment, anisotropic polarizability, as well as mean hyper-polarizability. Results show an increase with solvent polarity of these mentioned parameters, while mean polarizability decreases with increase in solvent polarity. On the other hand, the thermodynamic properties analysis unveiled that heat capacity and entropy increased with solvent polarity, whereas zero-point vibrational energy decreases with solvent polarity. This comprehensive investigation sheds light on the intricate interplay between solvent polarity and the structural, electronic, and thermodynamic properties of Salicylic acid, providing valuable insights for future studies in Physics, solvation Chemistry and Material science.
References
Abdulaziz, H., Gidado, A.S., Musa, A., 2019. Electronic Structure and Non-Linear Optical Properties of Neutral and Ionic Pyrene and Its Derivatives Based on Density Functional Theory. J. Mater. https://doi.org/10.9734/JMSRR/2019/45683
Akay, S., Kayan, B., Peña, M.Á., Jouyban, A., Martínez, F., 2023. Solubility of Salicylic Acid in Some (Ethanol + Water) Mixtures at Different Temperatures: Determination, Correlation, Thermodynamics and Preferential Solvation. Int. J. Thermophys. 44, 1–27. https://doi.org/10.1007/s10765-023-03224-z
An, C., Mou, Z., 2011. Salicylic Acid and its Function in Plant Immunity. J. Integr. Plant Biol. 53, 412–428. https://doi.org/10.1111/j.1744-7909.2011.01043.x
Arif, T., 2015. Salicylic acid as a peeling agent: A comprehensive review. Clin. Cosmet. Investig. Dermatol. 8, 455–461. https://doi.org/10.2147/CCID.S84765
Bálint, D., Jäntschi, L., 2021. Comparison of molecular geometry optimization methods based on molecular descriptors. Mathematics 9, 1–12. https://doi.org/10.3390/math9222855
Borah, M.M., Devi, T.G., 2018. Vibrational study and Natural Bond Orbital analysis of serotonin in monomer and dimer states by density functional theory. J. Mol. Struct. 1161, 464–476. https://doi.org/10.1016/j.molstruc.2018.02.055
El Ouafy, H., Aamor, M., Oubenali, M., Mbarki, M., Haimouti, A.E.L., El Ouafy, T., 2022. Theoretical study of the stability and reactivity of salicylic acid isomers by the DFT method. Curr. Chem. Lett. 11, 183–190. https://doi.org/10.5267/j.ccl.2022.2.002
Farajtabar, A., Gharib, F., 2010. Solvent effect on protonation constants of salicylic acid in mixed aqueous organic solutions of DMSO. Monatshefte fur Chemie 141, 381–386. https://doi.org/10.1007/s00706-010-0277-5
Gidado, A.S., Taura, L.S., Musa, A., 2021. Solvent Effects on The Electronic Structure and Non-Linear Optical Properties of Pyrene And Some Of Its Derivatives Based on Density Functional Theory. Fudma J. Sci. 4, 236–251. https://doi.org/10.33003/fjs-2020-0404-477
Grimes, P.E., 2006. Salicylic acid, Color Atlas of Chemical Peels. https://doi.org/10.1007/3-540-30223-9_6
HAMAD, O., OBAID KAREEM, R., KAYGILI, O., 2023. Density Function Theory Study of the Physicochemical Characteristics of 2-nitrophenol. J. Phys. Chem. Funct. Mater. 6, 70–76. https://doi.org/10.54565/jphcfum.1273771
HSSAIN, A., 2022. DFT modelling studies of spectroscopic properties and Medium Effects on Molecular Reactivity of Secnidazole in different solvents. J. Phys. Chem. Funct. Mater. 5, 69–83. https://doi.org/10.54565/jphcfum.1092855
Ismail, R.A., Suleiman, A.B., Gidado, A.S., Lawan, A., Musa, A., 2019. Investigation of the Effects of Solvents on the Structural, Electronic and Thermodynamic Properties of Rosiglitazone Based on Density Functional Theory. Phys. Sci. Int. J. 3, 1–18. https://doi.org/10.9734/psij/2019/v21i230103
Khan, M.F., Rashid, R. Bin, Hossain, M.A., Rashid, M.A., 2017. Computational study of solvation free energy, dipole moment, polarizability, hyperpolarizability and molecular properties of betulin, a constituent of Corypha taliera (Roxb.). Dhaka Univ. J. Pharm. Sci. 16, 1–9. https://doi.org/10.3329/dujps.v16i1.33376
Khezri, S., Jafari, P., Rahimpour, E., Jouyban, A., 2023. Enhancing the equilibrium solubility of salicylic acid in aqueous media by using polyethylene glycols 200, 400 and 600 as cosolvents: Correlation and dissolution thermodynamics. J. Chem. Thermodyn. 186, 107135. https://doi.org/10.1016/j.jct.2023.107135
Kiyooka, S.I., Kaneno, D., Fujiyama, R., 2013. Parr’s index to describe both electrophilicity and nucleophilicity. Tetrahedron Lett. 54, 339–342. https://doi.org/10.1016/j.tetlet.2012.11.039
Kumer, A., Ahmed, B., Sharif, M., Al-Mamun, A., 2017. A Theoretical Study of Aniline and Nitrobenzene by Computational Overview. Asian J. Phys. Chem. Sci. 4, 1–12. https://doi.org/10.9734/ajopacs/2017/38092
Lim, J., Jang, S., Cho, H.K., Shin, M.S., Kim, H., 2013. Solubility of salicylic acid in pure alcohols at different temperatures. J. Chem. Thermodyn. 57, 295–300. https://doi.org/10.1016/j.jct.2012.09.006
Maheshwari, S., Chowdhury, A., Sathyamurthy, N., Mishra, H., Tripathi, H.B., Panda, M., Chandrasekhar, J., 1999. Ground and Excited State Intramolecular Proton Transfer in Salicylic Acid: An Ab Initio Electronic Structure Investigation. J. Phys. Chem. A 103, 6257–6262. https://doi.org/10.1021/jp9911999
Marinho, M.M., Almeida-Neto, F.W.Q., Marinho, E.M., da Silva, L.P., Menezes, R.R.P.P.B., dos Santos, R.P., Marinho, E.S., de Lima-Neto, P., Martins, A.M.C., 2021. Quantum computational investigations and molecular docking studies on amentoflavone. Heliyon 7. https://doi.org/10.1016/j.heliyon.2021.e06079
Obi-Egbedi, N., Targema, M., Adeoye, M., Gbangban, S., 2015. Calculation of Electronic Properties of Some 4-Nitroaniline Derivatives: Molecular Structure and Solvent Effects. Int. Res. J. Pure Appl. Chem. 8, 165–174. https://doi.org/10.9734/irjpac/2015/18195
Onouchi, T., Watabe, T., Kinouchi, T., Shimizu, N., 1995. Salicylic acid, Nippon rinsho. Japanese journal of clinical medicine. https://doi.org/10.2165/00128415-201214310-00119
Oyeneyin, O., 2017. Structural and Solvent Dependence of the Electronic Properties and Corrosion Inhibitive Potentials of 1,3,4-thiadiazole and Its Substituted Derivatives- A Theoretical Investigation. Phys. Sci. Int. J. 16, 1–8. https://doi.org/10.9734/psij/2017/36555
Özokan, G., Sağır, T., Emekli-Alturfan, E., 2022. Synthesis of Natural Salicylic Acid as a Cosmetic Ingredient Using Green Chemistry Methods. Experimed 12, 12–17. https://doi.org/10.26650/experimed.2022.1068934
Parr, R.G., Szentpály, L. v., Liu, S., 1999. Electrophilicity Index. J. Am. Chem. Soc. 121, 1922–1924. https://doi.org/10.1021/ja983494x
Pegu, D., 2014. Solvent Effects on Nonlinear Optical Properties of Novel Para-nitroaniline Derivatives : A Density Functional Approach 3, 469–474.
Plakhutin, B.N., Davidson, E.R., 2009. Koopmans’ theorem in the restricted open-shell hartree-fock method. 1. A variational approach. J. Phys. Chem. A 113, 12386–12395. https://doi.org/10.1021/jp9002593
Sarasia, E.M., Soliman, M.E.S., Honarparvar, B., 2012. Theoretical study on the molecular electronic properties of salicylic acid derivatives as anti-inflammatory drugs. J. Struct. Chem. 53, 574–581. https://doi.org/10.1134/S0022476612030237
Sobolewski, A.L., Domcke, W., 2006. Photophysics of intramolecularly hydrogen-bonded aromatic systems: Ab initio exploration of the excited-state deactivation mechanisms of salicylic acid. Phys. Chem. Chem. Phys. 8, 3410–3417. https://doi.org/10.1039/b604610j
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. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc. 132, 130–141. https://doi.org/10.1016/j.saa.2014.04.174
Yang, W., Parr, R.G., 1985. Hardness, softness, and the fukui function in the electronic theory of metals and catalysis. Proc. Natl. Acad. Sci. U. S. A. 82, 6723–6726. https://doi.org/10.1073/pnas.82.20.6723
Downloads
Published
How to Cite
License
Copyright (c) 2025 MW Journal of Science
This work is licensed under a Creative Commons Attribution 4.0 International License.
