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The keto-enol tautomerism of 2-amino-4-pyrimidinol (APN) and 2-amino-pyrimidine-4(1H)-one (APO) are investigated by vibrational spectroscopy and quantum chemical method. FT-IR and FT-Raman spectra are recorded in the regions of 4000-400 cm-1 and 3500-100 cm-1, respectively for APN. Geometrical parameters, vibrational wavenumbers of APN and APO are predicted by density functional theory (DFT) employing B3LYP level with 6-311++G(d,p) and 6-311++G(2d,p) basis sets. The non-linear optical (NLO) properties of the title molecules are computed. The molecular electrostatic potential (MEP) surface maps are plotted and explained in detail. Natural bond orbital (NBO) analyses have been performed on APN molecule. The significant changes in occupancies and the energies of bonding and antibonding orbital have been explained in detail. Thermodynamic properties (heat capacities, entropies, and enthalpy) and their correlations with temperatures are also obtained from the calculated frequencies of the optimized structures. Reactivity descriptors, Fukui functions and electrophilic sites are found and discussed. © 2012 Elsevier B.V. All rights reserved.

Balachandran V.,Aa Government Arts College
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy | Year: 2013

In this work, the vibrational spectral analysis was carried out by FT-IR and FT-Raman spectroscopy in the regions of 4000-400 cm-1 and 3500-100 cm-1, respectively for 2′,4′- difluoroacetophenone (DFAP). The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on Hartree-Fock (HF), density functional theory (DFT) using B3LYP and LSDA methods with 6-31G basis set combination. The mixing of the fundamental modes was determined with the help of potential energy distribution (PED). The energies of the frontier molecular orbitals have also been determined. Complete NBO analysis was also carried out using B3LYP/6-31G level of theory to find out the intramolecular electronic interactions and their stabilization energy. Thermodynamic properties of the title compound were calculated at the different temperature. Finally, the calculation results were applied to simulate FT-IR and FT-Raman spectra of the title compound which show good agreement with observed spectra. © 2013 Elsevier B.V. All rights reserved.

The FT-IR and FT-Raman vibrational spectra of mesityl chloride (2,4,6-trimethylbenzyl chloride) were recorded. The optimized geometry and wavenumbers in the ground state were calculated using density functional (B3LYP, and B3PW91) methods with standard 6-311G(d,p) basis set. The computed B3PW91/6-311G(d,p) results show the best agreement with the experimental values over the other methods. Natural bond orbital analysis of mesityl chloride is also carried out, which confirms the occurrence of strong intermolecular bonding, stability of the molecule arising from hyperconjugative interactions, and charge delocalization. The electric dipole moment (μ), polarizability (α), and first hyperpolarizability (β 0) which results also show that the mesityl chloride might have microscopic non-linear optical behavior with non-zero values. The calculated HOMO and LUMO energies show that charge transfer occur in the molecule. The results of the calculations were applied to simulated spe ctra of the title compound, which show excellent agreement with observed spectra. © 2011 Elsevier B.V. All rights reserved.

Two purine tautomers of 2-amino-6-chloropurine (ACP), in labeled as N 9H10 and N7H10, were investigated by vibrational spectroscopy and quantum chemical method. The FT-IR and FT-Raman spectra of ACP have been recorded in the regions 4000-400 cm-1 and 3500-100 cm-1, respectively. The measured spectra were interpreted by aid of a normal coordinate analysis following DFT full geometry optimization and vibrational frequency calculations at B3LYP/6-311++G(d,p) level. First-order hyperpolarizability, HOMO and LUMO energies were calculated at same level of theory. The calculated molecular geometry has been compared with the X-ray data. The observed and calculated frequencies were found in good agreement. The obtained NBO data and second-order perturbation energy values to elucidate the Lewis and non-Lewis types of bonding structures in the purine tautomer N 9H10, have indicated the presence of an intramolecular hyperconjucative interaction between lone pair N and N-C bond orbital. © 2012 Elsevier B.V. All rights reserved.

Arivazhagan M.,Aa Government Arts College | Jeyavijayan S.,Alagappa Chettiar College of Engineering And Technology
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy | Year: 2011

The molecular vibrations of xanthine were investigated in polycrystalline sample, at room temperature by Fourier transform infrared (FTIR) and FT-Raman spectroscopies. The spectra of the molecule have been recorded in the regions 4000-50 cm-1 and 3500-100 cm-1, respectively. Theoretical information on the optimized geometry, harmonic vibrational frequencies, infrared and Raman intensities were obtained by means of ab initio Hartree-Fock (HF) and density functional theory (DFT) gradient calculations with complete relaxation in the potential energy surface using 6-311++G(d,p) basis set. The vibrational frequencies which were determined experimentally from the spectral data are compared with those obtained theoretically from ab initio and DFT calculations. A close agreement was achieved between the observed and calculated frequencies by refinement of the scale factors. The infrared and Raman spectra were also predicted from the calculated intensities. Thermodynamic properties like entropy, heat capacity, zero point energy have been calculated for the molecule. Unambiguous vibrational assignment of all the fundamentals was made using the potential energy distribution (PED). © 2010 Elsevier B.V. All rights reserved.

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