Exploration of electronic and vibrational properties of sulfanilic acid through periodic and non-periodic DFT calculations

Yasmine Slimani; Abdelali Boukaoud; Younes Chiba; Djamel Sebbar; Mohammed Ahmed Ammar; Abdelhak Ayad

doi:10.1007/s00894-024-05911-6

Exploration of electronic and vibrational properties of sulfanilic acid through periodic and non-periodic DFT calculations

J Mol Model. 2024 Apr 3;30(5):121. doi: 10.1007/s00894-024-05911-6.

Authors

Yasmine Slimani¹, Abdelali Boukaoud², Younes Chiba³, Djamel Sebbar¹, Mohammed Ahmed Ammar¹, Abdelhak Ayad^{4

5}

Affiliations

¹ Laboratory of Physics of Experimental Techniques and Their Applications, University of Medea, 26000, Medea, Algeria.
² Laboratory of Physics of Experimental Techniques and Their Applications, University of Medea, 26000, Medea, Algeria. boukaoud.abdelali@univ-medea.dz.
³ Renewable Energy and Materials Laboratory, Mechanical Engineering Department, University of Medea, 26000, Medea, Algeria.
⁴ Département de Pharmacie, Faculté de Médecine, Université Salah Boubnider Constantine 3, Nouvelle ville Ali Mendjeli, 25005, Constantine, Algeria.
⁵ Laboratoire Microstructures et Défauts dans les Matériaux, Univeristé Frères Mentouri Constantine 1, Route Ain El Bey, 25017, Constantine, Algeria.

PMID: 38570393
DOI: 10.1007/s00894-024-05911-6

Abstract

Context: The electronic, discrete water solvation, and vibrational properties of zwitterionic sulfanilic acid were thoroughly investigated using periodic and non-periodic DFT approaches. The periodic-DFT results, obtained by employing the PBE-TS functional (Perdew-Burke-Ernzerhof (PBE) functional with the Tkatchenko and Scheffler (TS) dispersion correction) were first presented in order to analyze the band structures of the studied crystal. An attentive reading of the predicted band structures has shown three lowest gap energies calculated at 4.23, 4.24, and 4.29 eV arising from the Γ→Γ, Γ→Z, and Γ→S transitions, respectively. Then, non-periodic calculations were carried out, at the B3LYP-D3 level of theory (B3LYP functional with the D3 Grimme dispersion correction) in order to optimize the sulfanilic acid-(H₂O)₁₀ complex. Starting from the optimized structure, non-covalent interaction calculations were performed and the H-bonding, van der Waals, and steric effect interactions were identified. Finally, the PBE-TS calculations were strengthened by conducting anharmonic B3LYP-D3 calculations in order to achieve a complete decryption of the experimental IR spectrum of sulfanilic acid. The spectral analysis is not limited only to the interpretation of both the NH/CH stretching and fingerprint regions but also extended to the 1800-2600 cm^-1 region, which is characterized by a strong anharmonic effect. In the latter wavenumber region, the large experimental IR band centered at 1937 cm^-1 is reproduced theoretically employing the anharmonic B3LYP-D3 calculations. The similarity of this band with those usually considered as a fingerprint of zwitterionic amino acids is observed, and its origin is elucidated theoretically. In the vibrational spectroscopy field, the calculations presented in this study are probably the most appropriate for achieving vast analysis and accurate assignments of vibrational spectra of hydrogen bonding compounds recorded in the solid state.

Method: The periodic and non-periodic calculations were conducted within the Density Functional Theory (DFT) using the Generalized Gradient Approximation (GGA) at the PBE-TS level of theory and B3LYP-D3 functional with the 6-311++G(d,p) basis set, respectively. The PBE-TS and B3LYP-D3/6-311++G(d,p) calculations were performed using the CASTEP and Gaussian 09 programs, respectively. In addition, The non-covalent interactions were calculated by the Multiwfn 3.8 software. The obtained results for different calculations were visualized by employing the visualization tools in Materials Studio, GaussView, VMD, and Gnuplot programs.

Keywords: Computational strategies; Harmonic and anharmonic calculations; IR spectroscopy; Periodic and non-periodic DFT calculations; Sulfanilic acid.