DFT STUDY OF ELECTRONIC PROPERTIES, SPECTROSCOPIC ANALYSIS, AND THERMODYNAMIC PARAMETERS OF CLEOMIN
DOI:
https://doi.org/10.3126/jist.v31i1.86526Keywords:
Cleomin, Density functional theory, electronic structure, vibrational analysis, thermodynamical parametersAbstract
Cleomin, a saturated heterocyclic and nonlinear organic molecule of pharmacological importance, yet it’s structural, electronic, and thermodynamic properties have not been adequately characterized at the molecular level. In this study, density functional theory calculations were performed at the B3LYP/6-311++G(d,p), WX97XD/6-311++G(d,p), and WX97XD/6-31++G(d,p) levels of theory, supplemented by a potential energy surface scan to understand the conformational stability of the Cleomin, whereas B3LYP/6-311++G(d,p) basis set was employed to examine the electronic behavior and thermodynamic properties of Cleomin. The optimized geometry of the Cleomin revealed a stable configuration with no imaginary frequencies. Non-covalent interaction - Reduced density gradient analysis identified dominant van der Waals interactions alongside weak hydrogen-bonding and steric repulsion within the ring system. The electron localization function and localized orbital locator maps showed a strong electron localization of electrons at hydrogen and sulphur atoms and the spatial distribution of bonding regions and lone pairs. The molecular electrostatic potential mapping showed electronegative regions around S1 and O2 as electrophilic attack sites and electropositive regions near nitrogen-bonded hydrogen as nucleophilic attack sites. Frontier molecular orbital analysis yielded an energy gap of 5.23 eV, confirmed by the density of states spectrum, indicating chemical stability and low reactivity. Mulliken charge analysis identified S1 and H17 as the primary reactive centers. Natural bonding orbital analysis revealed strong hyper-conjugative interaction from N3[LP(1)] to S1-C9(σ∗) with a stabilization energy of 68.90 kcal/mol, and Fukui function analysis clearly distinguished sites for nucleophilic and electrophilic attack. Vibrational wavenumbers showed excellent agreement with reported FT-IR data, and thermodynamic parameters (i.e., Specific heat capacity, Entropy and Enthalpy) increased consistently with rising temperature. These findings offer a valuable foundation for the potential applications of Cleomin in drug design and medicinal chemistry.
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