Browsing by Author "Govindarajan M."

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    FT-IR, FT-Raman and UV spectral investigation; Computed frequency estimation analysis and electronic structure calculations on 4-hydroxypteridine
    (2013) Govindarajan M.; Karabacak M.
    In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 100-4000 cm-1 and 400-4000 cm-1 respectively, for 4-hydroxypteridine (C 6H4N4O, 4HDPETN) molecule. The potential energy curve shows that 4HDPETN molecule has two stable structures. The computational results diagnose the most stable conformer of the 4HDPETN as the S1 structure. The molecular structure, fundamental vibrational frequencies and intensities of the vibrational bands were interpreted with the aid of structure optimizations and normal coordinate force field calculations based density functional theory (DFT) and ab initio HF methods and different basis sets combination. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra. The scaled B3LYP/6-311++G(d,p) results show the best agreement with the experimental values over the other method. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) complements with the experimental findings. In addition, molecular electrostatic potential, nonlinear optical and thermodynamic properties of the title compound were performed. Mulliken and natural charges of the title molecule were also calculated and interpreted. © 2013 Elsevier B.V. All rights reserved.
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    Spectroscopic (FT-IR, FT-Raman and NMR) and computational studies on 3-methoxyaniline
    (2014) Sivaranjini T.; Periandy S.; Govindarajan M.; Karabacak M.; Asiri A.M.
    In this work, the molecular structure, vibrational, UV and NMR spectra of 3-methoxyaniline (abbreviated as 3MOA, C7H9NO) were studied. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies were calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d, p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3MOA with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, Frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed and compared with methoxybenzene and aniline. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 3MOA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. © 2013 Elsevier B.V. All rights reserved.
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    Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations
    (Elsevier, 2015) Nagabalasubramanian P.B., Ekrubha@yahoo.com; Periandy S.; Karabacak M.; Govindarajan M.
    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.