Structural and spectroscopic characterization of 2,3-difluorobenzoic acid and 2,4-difluorobenzoic acid with experimental techniques and quantum chemical calculations

In this study, the molecular conformation, vibrational and electronic transition analysis of 2,3-difluorobenzoic acid and 2,4-difluorobenzoic acid (C7H4F2O2) were presented using experimental techniques (FT-IR, FT-Raman and UV) and quantum chemical calculations. FT-IR and FT-Raman spectra in solid state were recorded in the region 4000-400 cm(-1) and 4000-5 cm(-1), respectively. The UV absorption spectra of the compounds that dissolved in ethanol were recorded in the range of 200-800 nm. The structural properties of the molecules in the ground state were calculated using density functional theory (DFT) and second order M?ller-Plesset perturbation theory (MP2) employing 6-311++G(d,p) basis set. Optimized structure of compounds was interpreted and compared with the earlier reported experimental values. The scaled vibrational wavenumbers were compared with experimental results. The complete assignments were performed on the basis of the experimental data and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. A study on the electronic properties, such as absorption wavelength, excitation energy, dipole moment and frontier molecular orbital energy, were performed by time dependent DFT (TD-DFT) approach. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands of steady compounds were discussed. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecules.     

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.     

NMR, UV, FT-IR, FT-Raman spectra and molecular structure (monomeric and dimeric structures) investigation of nicotinic acid N-oxide: A combined experimental and theoretical study

In this work, the experimental and theoretical UV, NMR, and vibrational features of nicotinic acid N-oxide (abbreviated as NANO, C(6)H(5)NO(3)) were studied. The ultraviolet (UV) absorption spectrum of studied compound that dissolved in water was examined in the range of 200-800nm. FT-IR and FT-Raman spectra in solid state were observed in the region 4000-400cm(-1) and 3500-50cm(-1), respectively. The (1)H and (13)C NMR spectra in DMSO were recorded. The geometrical parameters, energies and the spectroscopic properties of NANO were obtained for all four conformers from density functional theory (DFT) B3LYP/6-311++G(d,p) basis set calculations. There are four conformers, C(n), n=1-4 for this molecule. The computational results identified the most stable conformer of title molecule as the C1 form. The complete assignments were performed on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. (13)C and (1)H nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by using the gauge-invariant atomic orbital (GIAO) method. The electronic properties, such as excitation energies, absorption wavelengths, HOMO and LUMO energies, were performed by CIS approach. Finally the calculation results were applied to simulate infrared, Raman, and UV spectra of the title compound which show good agreement with observed spectra.     

Experimental (FT-IR and FT-Raman), electronic structure and DFT studies on 1-methoxynaphthalene

In this work, FT-IR and FT-Raman spectra of 1-methoxynapthalene (C(11)H(10)O) have been reported in the regions 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Density functional method (DFT) has been used to calculate the optimized geometrical parameters, atomic charges, vibrational wavenumbers and intensity of the vibrational bands. The vibrational frequencies have been calculated and scaled values are compared with experimental FT-IR and FT-Raman spectra. The structure optimizations and normal coordinate force field calculations are based on density functional theory (DFT) method with B3LYP/3-21G, B3LYP/6-31G, B3LYP/6-31G(d,p) and B3LYP/6-311++G(d,p) basis sets. The complete vibrational assignments of wavenumbers are made on the basis of potential energy distribution (PED). The optimized geometric parameters are compared with experimental values of naphthoic acid. The results of the calculation shows excellent agreement between experimental and calculated frequencies in B3LYP/6-311++G(d,p) basis set. The effects due to the substitutions of methyl group and carbon-oxygen bond are also investigated. A study on the electronic properties, such as excitation energies and wavelengths, were performed by time-dependent DFT (TD-DFT) approach. HOMO and LUMO energies are calculated that these energies show charge transfer occurs within the molecule.     

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.     

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.     

Experimental and theoretical investigations of benzamide oxime

The FT-IR (4000-400 cm(-1)) and FT-Raman (4000-100 cm(-1)) spectral measurements of benzamide oxime and complete assignments of the observed spectra have been proposed. Ab initio and DFT calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, depolarization ratios, IR intensities, Raman activities and atomic displacements. Furthermore, force field calculations have been performed by normal coordinate analysis. Force field calculations showed that several normal modes are mixed in terms of the internal coordinates. A complete assignment of the observed spectra, based on spectral correlations, electronic structure calculations and normal coordinate analysis, has been provided.     

Vibrational spectroscopy (FT-IR and FT-Raman) investigation, and hybrid computational (HF and DFT) analysis on the structure of 2,3-naphthalenediol

The FT-IR and FT-Raman vibrational spectra of 2,3-naphthalenediol (C(10)H(8)O(2)) have been recorded using Bruker IFS 66V spectrometer in the range of 4000-100 cm(-1) in solid phase. A detailed vibrational spectral analysis has been carried out and the assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The optimized molecular geometry and vibrational frequencies in the ground state are calculated by using the ab initio Hartree-Fock (HF) and DFT (LSDA and B3LYP) methods with 6-31+G(d,p) and 6-311+G(d,p) basis sets. There are three conformers, C1, C2 and C3 for this molecule. The computational results diagnose the most stable conformer of title molecule as the C1 form. The isotropic computational analysis showed good agreement with the experimental observations. Comparison of the fundamental vibrational frequencies with calculated results by HF and DFT methods. Comparison of the simulated spectra provides important information about the capability of computational method to describe the vibrational modes. A study on the electronic properties, such as absorption wavelengths, excitation energy, dipole moment and Frontier molecular orbital energies, are performed by time dependent DFT approach. The electronic structure and the assignment of the absorption bands in the electronic spectra of steady compounds are discussed. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. On the basis of the thermodynamic properties of the title compound at different temperatures have been calculated. The statistical thermodynamic properties (standard heat capacities, standard entropies, and standard enthalpy changes) and their correlations with temperature have been obtained from the theoretical vibrations.     

Vibrational spectroscopic (FT-IR and FT-Raman), first-order hyperpolarizablity, HOMO, LUMO, NBO, Mulliken charges and structure determination of 2-bromo-4-chlorotoluene

The FT-IR and FT-Raman spectra of 2-bromo-4-chlorotoluene (2B4CT) molecule have been recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1), respectively. Optimized geometrical structures, harmonic vibrational frequencies, intensities, reduced mass, force constants and depolarization ratio have been computed by the B3 based (B3LYP) density functional methods using 6-31+G(d,p) and 6-311++G(d,p) basis sets. The observed FT-IR and FT-Raman vibrational frequencies are analysed and compared with theoretically predicted vibrational frequencies. The geometries and normal modes of vibration obtained from DFT method are in good agreement with the experimental data. The Mulliken charges, the natural bonding orbital (NBO) analysis, the values of electric dipole moment (μ) and the first-order hyperpolarizability (β) of the investigated molecule were computed using DFT calculations. The calculated HOMO and LUMO energies show that charge transfer occurs within molecule. The influences of bromine atom, chlorine atom and methyl group on the geometry of benzene and its normal modes of vibrations have also been discussed.     

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.     

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.     

Vibrational spectroscopic, first-order hyperpolarizability and HOMO, LUMO studies of 1,2-dichloro-4-nitrobenzene based on Hartree-Fock and DFT calculations

The Fourier-transform infrared spectrum of 1,2-dichloro-4-nitrobenzene (DCNB) was recorded in the region 4000-400cm(-1). The Fourier-transform Raman spectrum of DCNB was also recorded in the region 3500-50cm(-1). Quantum chemical calculations of energies, geometrical structure and vibrational wavenumbers of DCNB were carried out by ab initio HF and density functional theory (DFT/B3LYP) method with 6-31+G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The values of the total dipole moment (μ) and the first-order hyperpolarizability (β) of the investigated compound were computed using ab initio quantum mechanical calculations. The calculated results also show that the DCNB might have microscopic nonlinear optical (NLO) behavior with non-zero values. A detailed interpretation of the infrared and Raman spectra of DCNB is also reported based on total energy distribution (TED). The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The theoretical FT-IR and FT-Raman spectra for the title compound have also been constructed.     

Vibrational spectroscopy investigation using ab initio and density functional theory analysis on the structure of 3,4-dimethylbenzaldehyde

The FT-IR and FT-Raman spectra of 3,4-dimethylbenzaldehyde (3,4-DMB) has been recorded in the region 4000-400 and 3500-100 cm(-1), respectively. The optimized geometry, frequency and intensity of the vibrational bands of 3,4-DMB were obtained by the ab initio and DFT levels of theory with complete relaxation in the potential energy surface using 6-311G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar type spectrograms.     

Molecular structure, vibrational spectroscopic (FT-IR, FT-Raman), UV and NBO analysis of 2-chlorobenzonitrile by density functional method

In this work, we will report a combined experimental and theoretical study on molecular structure, vibrational spectra, NBO and UV spectral analysis of 2-chlorobenzonitrile (2-ClBN). The FT-IR solid phase (4000-400 cm(-1)), and FT-Raman spectra (3500-50 cm(-1)) of 2-ClBN was recorded. The molecular geometry, harmonic vibrational frequencies and bonding features of 2-ClBN in the ground state have been calculated by using the density functional methods (BLYP, B3LYP) with 6-31G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field Methodology (SQMFF). Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The results show that charge in electron density (ED) in the σ* and π* anti bonding orbitals and E2 energies confirms the occurrence of ICT (Intra molecular Charge Transfer) within the molecule. The UV spectrum was measured in ethanol solution. The energy and oscillator strength calculated by Time-Dependent Density Functional Theory (TD-DFT) results complements with the experimental findings. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. Finally calculated results were applied to simulated Infrared and Raman spectra of the title compound which show good agreement with observed spectra.     

Experimental (FT-IR and FT-Raman) and theoretical (HF and DFT) investigation, IR intensity, Raman activity and frequency estimation analyses on 1-bromo-4-chlorobenzene

The FT-IR and FT-Raman spectra of 1-bromo-4-chlorobenzene (1-Br-4-CB) have been recorded using Bruker IFS 66V spectrometer in the region of 4000-100 cm(-1). Ab-initio-HF (HF/6-311+G (d, p)) and DFT (B3LYP/6-31++G (d, p)/6-311++G (d, p)) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, depolarization ratios, IR intensities, Raman activities. The vibrational frequencies are calculated and scaled values are compared with FT-IR and FT-Raman experimental values. Comparison of simulated spectra with the experimental spectra provides important information, the computational method have the ability to describe the vibrational methods. The frequency estimation analysis on HF and DFT is made. The impact of di-substituted halogens on the benzene molecule has also been discussed.     

FT-IR, FT-Raman spectra and ab initio HF, DFT vibrational analysis of 2,3-difluoro phenol

The FT-IR and FT-Raman spectra of 2,3-difluoro phenol (2,3-DFP) has been recorded in the region 4000-400 and 4000-100 cm(-1), respectively. The optimized geometry, frequency and intensity of the vibrational bands of 2,3-DFP were obtained by the ab initio HF and density functional theory (DFT) levels of theory with complete relaxation in the potential energy surface using 6-311+G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with experimental FT-IR and FT-Raman spectra. The observed and the calculated frequencies are found to be in good agreement. The experimental spectra also coincide satisfactorily with those of theoretically constructed bar type spectrograms.     

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.     

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.     

FT-IR and FT-Raman, UV spectroscopic investigation of 1-bromo-3-fluorobenzene using DFT (B3LYP, B3PW91 and MPW91PW91) calculations

The FT-IR and FT-Raman spectra of 1-bromo-3-fluorobenzene (C₆H₄FBr) molecule have been recorded using Bruker IFS 66 V spectrometer in the range of 4000–100 cm⁻¹. The molecular geometry and vibrational frequencies in the ground state are calculated using the DFT (B3LYP, B3PW91 and MPW91PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets. The computed values of frequencies are scaled using a suitable scale factor to yield good coherence with the observed values. The isotropic DFT (B3LYP, B3PW91 and MPW1PW91) analysis showed good agreement with the experimental observations. Comparison of the fundamental vibrational frequencies with calculated results by B3LYP methods. The complete data of this molecule provide the information for future development of substituted benzene. The influence of bromine and fluorine atom on the geometry of benzene and its normal modes of vibrations has also been discussed. A study on the electronic properties, such as absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, was performed by time dependent DFT (TD-DFT) approach. The electronic structure and the assignment of the absorption bands in the electronic spectra of steady compounds were discussed. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. On the basis of the thermodynamic properties of the title compound at different temperatures have been calculated in gas phase, revealing the correlations between standard heat capacities (C) standard entropies (S), standard enthalpy changes (H) and temperatures.