Density functional theory study on the identification of 3-[(2-morpholinoethylimino)methyl]benzene-1,2-diol

This study deals with the identification of a title compound, 3-[(2-morpholinoethylimino)methyl]benzene-1,2-diol by means of quantum chemical calculations. The optimized molecular structures, vibrational frequencies and corresponding vibrational assignments, thermodynamic properties, charge analyses, nuclear magnetic resonance (NMR) chemical shifts and ultraviolet-visible (UV-vis) spectra of the title molecule in the ground state were evaluated using density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra of the title compound were interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results show that the obtained optimized geometric parameters (bond lengths, bond angles and bond dihedrals) and vibrational frequencies were observed to be in good agreement with the available experimental results. Moreover, the calculations of the electronic spectra, (13)C and (1)H chemical shifts were compared with the experimental ones. Furthermore, we not only simulated the frontier molecular orbitals (FMO) and molecular electrostatic potential (MEP) but also determined the transition states and energy band gaps, as well. It was found that charge analyses supported the evidences of MEP. Infrared intensities and Raman activities were also reported.     

FT-IR, FT-Raman, NMR and UV-vis spectra, vibrational assignments and DFT calculations of 4-butyl benzoic acid

The solid phase FTIR and FT-Raman spectra of 4-butyl benzoic acid (4-BBA) have been recorded in the regions 400-4000 and 50-4000cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-311++G(d,p) as basis set. The vibrational frequencies were calculated for monomer and dimer by DFT method and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. (13)C and (1)H NMR spectra were recorded and (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was recorded in the region 200-400nm and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman intensities, chemical shifts and absorption wavelengths were compared with the available experimental data of the molecule.     

A study on quantum chemical calculations of 3-, 4-nitrobenzaldehyde oximes

The molecular geometry, vibrational frequencies, 1H and 13C NMR chemical shifts, UV-vis spectra, HOMO-LUMO analyses, molecular electrostatic potentials (MEPs), , thermodynamic properties and atomic charges of 3- and 4-Nitrobenzaldehyde oxime (C7H6N2O3) molecules have been investigated by using Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with the 6-311++G(d, p) basis set. The calculated optimized geometric parameters (bond lengths and bond angles), the vibrational frequencies calculated and 13C and 1H NMR chemical shifts values for the mentioned compounds are in a very good agreement with the experimental data. Furthermore, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) have been simulated and the transition states, energy band gaps and molecular electrostatic potential (MEP) maps for each oxime compound have been determined. Additionally, we also report the infrared intensities and Raman activities for the compounds under study.     

Theoretical investigations of α,α,α-trifluoro-3, -p and o-nitrotoluene by means of density functional theory

This study reports the optimized molecular structures, vibrational frequencies including Infrared intensities and Raman activities, corresponding vibrational assignments, (1)H and (13)C NMR chemical shifts, the magnitudes of the JCH and JCC coupling constants, Ultraviolet-visible (UV-vis) spectra, thermodynamic properties and atomic charges of the title compounds, α,α,α-trifluoro-3, -p and o-nitrotoluene, in the ground state by means of the density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra were interpreted by normal coordinate analysis based on scaled density functional force field. The results show that the vibrational frequencies and chemical shifts calculated were obtained to be in good agreement with the experimental data. Based on the comparison between experimental results and theoretical data, the calculation level chosen is powerful approach for understanding the identification of all the molecules studied. In addition, not only were frontier molecular orbitals (HOMO and LUMO), molecular electrostatic potential (MEP) and electrostatic potential (ESP) simulated but also the dipole moment, softness, electronegativity, chemical hardness, electrophilicity index, transition state and energy band gap values were predicted. According to the investigations, all compounds were found to be useful to bond metallically and interact intermolecularly; however, the thermodynamic properties confirm that the α,α,α-trifluoro-p-nitrotoluene was more reactive and more polar than the others.     

FT-IR, UV-vis, 1H and 13C NMR spectra and the equilibrium structure of organic dye molecule disperse red 1 acrylate: a combined experimental and theoretical analysis

This study reports the characterization of disperse red 1 acrylate compound by spectral techniques and quantum chemical calculations. The spectroscopic properties were analyzed by FT-IR, UV-vis, (1)H NMR and (13)C NMR techniques. FT-IR spectrum in solid state was recorded in the region 4000-400 cm(-1). The UV-vis absorption spectrum of the compound that dissolved in methanol was recorded in the range of 200-800 nm. The (1)H and (13)C NMR spectra were recorded in CDCl(3) solution. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR spectrum. A satisfactory consistency between the experimental and theoretical spectra was obtained and it shows that the hybrid DFT method is very useful in predicting accurate vibrational structure, especially for high-frequency region. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties were performed by timedependent DFT (TD-DFT) and CIS(D) approach. To investigate non linear optical properties, the electric dipole moment μ, polarizability α, anisotropy of polarizability Δα and molecular first hyperpolarizability β were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the compound can be a good candidate of nonlinear optical materials.     

Experimental and theoretical investigation of the molecular and electronic structure of anticancer drug camptothecin

The Fourier Transform Infrared spectrum of (S)-4 ethyl-4-hydroxy-1H-pyrano [3',4':6,7]-indolizino-[1,2-b-quinoline-3,14-(4H,12H)-dione] [camptothecin] was recorded in the region 4000-400 cm(-1). The Fourier Transform Raman spectrum of camptothecin (CPT) was also recorded in the region 3500-50 cm(-1). Quantum chemical calculations of geometrical structural parameters and vibrational frequencies of CPT were carried out by MP2/6-31G(d,p) and density functional theory DFT/B3LYP/6-311++G(d,p) methods. The assignment of each normal mode has been made using the observed and calculated frequencies, their IR and Raman intensities. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. Most of the computed frequencies were found to be in good agreement with the experimental observations. The isotropic chemical shifts computed by (13)C and (1)H NMR analysis also show good agreement with experimental observations. Comparison of calculated spectra with the experimental spectra provides important information about the ability of computational method to describe the vibrational modes of large sized organic molecule.     

FT-IR, FT-Raman and UV spectral investigation; computed frequency estimation analysis and electronic structure calculations on 1-nitronaphthalene

In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 100-4000cm(-1) and 400-4000cm(-1) respectively, for 1-nitronaphthalene (C(10)H(7)NO(2)) molecule. 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 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 total energy distribution (TED). 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 methods. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) complements with the experimental findings. Thermodynamic properties of the title compound at different temperatures have been calculated. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) were performed.     

Intramolecular hydrogen bond, molecular structure and vibrational assignment of tetra-acetylethane. A density functional study

The intramolecular hydrogen bond, molecular structure and vibrational frequencies of tetra-acetylethane have been investigated by means of high-level density functional theory (DFT) methods with most popular basis sets. Fourier transform infrared and Fourier transform Raman spectra of this compound and its deuterated analogue were recorded in the regions 400-4000 cm(-1) and 40-4000 cm(-1), respectively. The calculated geometrical parameters of tetra-acetylethane were compared to the experimental results of this compound and its parent molecule (acetylacetone), obtained from X-ray diffraction. The O...O distance in tetra-acetylethane, about 2.424A, suggests that the hydrogen bond in this compound is stronger than acetylacetone. This conclusion is well supported by the NMR proton chemical shifts and O-H stretching mode at 2626 cm(-1). Furthermore, the calculated hydrogen bond energy in the title compound is 17.22 kcal/mol, which is greater than the acetylacetone value. On the other hand, the results of theoretical calculations show that the bulky substitution in alpha-position of acetylacetone results in an increase of the conjugation of pi electrons in the chelate ring. Finally, we applied the atoms in molecules (AIM) theory and natural bond orbital method (NBO) for detail analyzing the hydrogen bond in tetra-acetylethane and acetylacetone. These results are in agreement with the vibrational spectra interpretation and quantum chemical calculation results. Also, the conformations of methyl groups with respect to the plane of the molecule and with respect to each other were investigated.     

Spectral analysis of acetylcholine halides by density functional theory calculations

The optimized molecular structures, vibrational frequencies and ¹H and ¹³C NMR chemical shifts of acetylcholine halides (F, Cl, and Br) have been investigated using density functional theory (B3LYP) method with 6-311G(d) basis set. The comparison of their experimental and calculated IR, R and NMR spectra of the compounds has indicated that the spectra of three optimized minimum energy conformers can simultaneously exist in one experimental spectrum. Thus, it was concluded that the compounds simultaneously exist in three conformations in the ground state. The calculated optimized geometric parameters (bond lengths and bond angles), vibrational frequencies and NMR chemical shifts for the minimum energy conformers were seen to be in a good agreement with the corresponding experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program.     

Synthesis,molecular conformation,vibrational, electronic transition,and chemical shift assignments of 4-(thiophene-3-ylmethoxy)phthalonitrile: a combined experimental and theoretical analysis

This work presents the synthesis and characterization of a novel compound, 4-(thiophene-3-ylmethoxy)phthalonitrile (TMP). The spectroscopic properties of the compound were examined by FT-IR, FT-Raman, NMR, and UV techniques. FT-IR and FT-Raman spectra in solid state were observed in the region 4000–400 cm⁻¹ and 3500–50 cm⁻¹, respectively. The ¹H and ¹³C NMR spectra were recorded in CDCl₃ solution. The UV absorption spectrum of the compound that dissolved in THF was recorded in the range of 200–800 nm. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR and FT-Raman spectra. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts (¹³C NMR and ¹H NMR) were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The HOMO and LUMO analyses have been used to elucidate information regarding charge transfer within the molecule. Comparison of the calculated frequencies, NMR chemical shifts, absorption wavelengths with the experimental values revealed that DFT method produces good results.     

Experimental, theoretical calculations of the vibrational spectra and conformational analysis of 2,4-di-tert-butylphenol

In the present work, we reported a combined experimental and theoretical study on conformational stability, molecular structure and vibrational spectra of 2,4-di-tert-butylphenol (2,4-DTBP). The FT-IR (400-4000cm(-1)) and FT-Raman spectra (50-3500cm(-1)) of 2,4-DTBP were recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of 2,4-DTBP in the ground-state have been calculated by using the density functional BLYP/B3LYP methods. The energy calculated by time-dependent density functional theory (TD-DFT) result complements with the experimental findings. The calculated highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies show that charge transfer occurs within the molecule. Finally the calculation results were compared with measured infrared and Raman spectra of the title compound which showed good agreement with observed spectra.     

Molecular structure, vibrational spectral studies of pyrazole and 3,5-dimethyl pyrazole based on density functional calculations

In this work, the experimental and theoretical vibrational spectra of pyrazole (PZ) and 3,5-dimethyl pyrazole (DMP) have been studied. FTIR and FT-Raman spectra of the title compounds in the solid phase are recorded in the region 4000-400 cm(-1) and 4000-50 cm(-1), respectively. The structural and spectroscopic data of the molecules in the ground state are calculated using density functional methods (B3LYP) with 6-311+G** basis set. The vibrational frequencies are calculated and scaled values are compared with experimental FTIR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete vibrational assignments are performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanical (SM) method. 13C and 1H NMR chemical shifts results are compared with the experimental values.     

Multi spectroscopic and computational investigations on the electronic structure of oxyclozanide

The present work contributes to a combined theoretical and experimental investigation on oxyclozanide. The experimental vibrational spectra were characterized by Fourier transform infrared (4000-400 cm^?1), Fourier transform Raman (4000-400 cm^?1), ¹H and ¹³C NMR were recorded in Deuterated methanol, UV–Vis (200–400 nm) techniques and theoretical optimized molecular geometry, harmonic vibrational spectra, magnetic spectra, and electronic spectra was calculated by Density Functional Theory (DFT) employed with B3LYP/6-311++G(d,p) basis set and compared with experimental data. The highest occupied molecular orbital - lowest unoccupied molecular orbital (HOMO-LUMO) energy was also calculated for the titled compound. The intermolecular interactions have been addressed through Hirshfeld surface analysis. In addition, Natural bond orbital (NBO) analyses of the title compound were performed to evaluate the suitable reactivity site and chemical stabilization behavior, Mulliken atomic charge distribution, and molecular electrostatic potential energy surfaces, were calculated to get a better insight into the structure of oxyclozanide. The experimental and theoretical findings suggest an excellent correlation to confirm the structure of oxyclozanide.     

Molecular structure, vibrational, UV and NBO analysis of 4-chloro-7-nitrobenzofurazan by DFT calculations

In the present work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of 4-chloro-7-nitrobenzofurazan (NBD-Chloride). The FT-IR (400-4000 cm(-1)) and FT-Raman spectra (50-4000 cm(-1)) of NBD-Chloride were recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of NBD-Chloride in the ground-state have been calculated by using the density functional B3LYP method with 6-311++G (d, p) as higher basis set. The energy and oscillator strength calculated by time-dependent density functional theory (TD-DFT) result in DMSO and CDCl3 solvents complements with each other. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. Finally the calculation results were applied to simulate infrared and Raman spectra of the title compound which show good agreement with observed spectra.     

A characterization study on 2,6-dimethyl-4-nitropyridine N-oxide by density functional theory calculations

This study deals with the identification of a title compound, 2,6-dimethyl-4-nitropyridine N-oxide by means of theoretical calculations. The optimized molecular structures, vibrational frequencies, corresponding vibrational assignments, thermodynamic properties and atomic charges of the title compound in the ground state were evaluated using density functional theory (DFT) with the standard B3LYP/6-311G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra were interpreted with the aid of normal coordinate analysis based on scaled density functional force field. The results show that the optimized geometric parameters (bond lengths and bond angles) and vibrational frequencies were observed to be in good agreement with the available experimental results. Based on the results of comparison between experimental results and theoretical data, the chosen calculation level is powerful approach for understanding the molecular structures and vibrational spectra of the 2,6-dimethyl-4-nitropyridine N-oxide. Moreover, we not only simulated frontier molecular orbitals (FMO) and molecular electrostatic potential (MEP) but also determined the transition state and energy band gap. Based on the investigations, the title compound is found to be useful to bond metallically and interact intermolecularly. Infrared intensities and Raman activities were also reported.     

FT-IR,FT-Raman,NMR spectra and DFT calculations on 4-chloro-N-methylaniline

In this work, the vibrational spectral analysis was carried out by using FT-IR and FT-Raman spectroscopy in the range 400–4000 and 50–3500 cm^?1 respectively, for the title molecule. The structural and spectroscopic data of the molecule in the ground state were calculated by using density functional method using 6-311++G(d,p) basis set. The vibrational frequencies were calculated and scaled values were compared with experimental FT-IR and FT-Raman spectra. The observed and calculated frequencies are found to be in good agreement. The complete assignments of all the vibrational mode were performed on the basis of the total energy distributions (TED). ¹³C and ¹H NMR chemical shifts results were given and are in agreement with the corresponding experimental values. The theoretically constructed FT-IR and FT-Raman spectra exactly coincides with experimental one.     

Spectroscopic (NMR, UV, FT-IR and FT-Raman) analysis and theoretical investigation of nicotinamide N-oxide with density functional theory

The spectroscopic properties of the nicotinamide N-oxide (abbreviated as NANO, C(6)H(6)N(2)O(2)) were examined by FT-IR, FT-Raman, NMR and UV techniques. FT-IR and FT-Raman spectra in solid state were observed in the region 4000-400 cm(-1) and 3500-50 cm(-1), respectively. The (1)H and (13)C NMR spectra were recorded in DMSO. The UV absorption spectrum of the compound that dissolved in water was recorded in the range of 200-800 nm. The structural and spectroscopic data of the molecule in the ground state were calculated by using Density Functional Theory (DFT) employing B3LYP methods with the 6-311++G(d,p) basis set. The geometry of the molecule was fully optimized, vibrational spectra were calculated and 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. The optimized structure of compound was interpreted and compared with the reported experimental values. The observed vibrational wavenumbers, absorption wavelengths and chemical shifts were compared with calculated values. As a result, the optimized geometry and calculated spectroscopic data show a good agreement with the experimental results.     

Vibrational investigation, molecular orbital studies and molecular electrostatic potential map analysis on 3-chlorobenzoic acid using hybrid computational calculations

The FT-IR and FT-Raman spectra of 3-chlorobenzoic acid (3CBA) are recorded in the liquid state. The fundamental vibrational frequencies, intensity of vibrational bands and the optimized geometrical parameters of the compound are evaluated using HF and DFT (LSDA/B3LYP/B3PW91/MPW1PW91) methods with 6-311+G(d,p) basis set. The theoretical wave numbers are scaled down and compared with the experimental values which showed very good agreement. Comparison of stimulated spectra with the experimental spectra provides important information about the ability of the hybrid computational method to describe the vibrational modes. The HOMO, LUMO, chemical hardness (η), chemical potential (μ), electrophilicity values (ω) and maximum amount of electronic charge transfer (ΔN(max)) are calculated. The molecular electrostatic potential (MESP) is calculated and the corresponding graphs are drawn. Some thermodynamic parameters and physico-chemical properties are calculated and discussed.     

Synthesis, molecular conformation, vibrational and electronic transition, isometric chemical shift, polarizability and hyperpolarizability analysis of 3-(4-methoxy-phenyl)-2-(4-nitro-phenyl)-acrylonitrile: a combined experimental and theoretical analysis

This work presents the synthesis and characterization of a novel compound, 3-(4-Methoxy-phenyl)-2-(4-nitro-phenyl)-acrylonitrile (abbreviated as 3-(4MP)-2-(4-NP)-AN, C₁₆H₁₂N₂O₃). The spectroscopic properties of the compound were examined by FT-IR, UV–vis and NMR (¹H and ¹³C) techniques. FT-IR spectrum in solid state was observed in the region 4000–400 cm⁻¹. The UV–vis absorption spectrum of the compound which dissolved in chloroform was recorded in the range of 200–800 nm. The ¹H and ¹³C NMR spectra were recorded in CDCl₃ solution. To determine lowest-energy molecular conformation of the title molecule, the selected torsion angle is varied every 10° and molecular energy profile is calculated from 0° to 360°. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP/6-31G(d,p) basis set. The dipole moment, linear polarizability and first hyperpolarizability values were also computed using the same basis set. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The HOMO and LUMO analysis were used to elucidate information regarding charge transfer within the molecule. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR spectrum. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. Comparison of the calculated frequencies, NMR chemical shifts, absorption wavelengths with the experimental values revealed that DFT and TD-DFT method produce good results. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the title compound can be used as a good nonlinear optical material. The thermodynamic properties of the studied compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures.     

Experimental and theoretical studies on vibrational spectra of 4-(2-furanylmethyleneamino)antipyrine, 4-benzylideneaminoantipyrine and 4-cinnamilideneaminoantipyrine

This work deals with the IR and Raman spectroscopy of 4-(2-furanylmethyleneamino) antipyrine (FAP), 4-benzylideneaminoantipyrine (BAP) and 4-cinnamilideneaminoantipyrine (CAP) by means of experimental and quantum chemical calculations. The equilibrium geometries, harmonic frequencies, infrared intensities and Raman scattering activities were calculated by density functional B3LYP method with the 6-31G(d) basis set. The comparisons between the calculated and experimental results covering molecular structures, assignments of fundamental vibrational modes and thermodynamic properties were investigated. The optimized molecular geometries have been compared with the experimental data obtained from XRD data, which indicates that the theoretical results agree well with the corresponding experimental values. For the three compounds, comparisons and assignments of the vibrational frequencies indicate that the calculated frequencies are close to the experimental data, and the IR spectra are comparable with some slight differences, whereas the Raman spectra are different clearly and the strongest Raman scattering actives are relative tightly to the molecular conjugative moieties linked through their Schiff base imines. The thermodynamic properties (heat capacities, entropies and enthalpy changes) and their correlations with temperatures were also obtained from the harmonic frequencies of the optimized strucutres.