Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-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.

Spectroscopic analysis of cinnamic acid using quantum chemical calculations.

In this present study, FT-IR, FT-Raman, (13)C NMR and (1)H NMR spectra for cinnamic acid have been recorded for the vibrational and spectroscopic analysis. The observed fundamental frequencies (IR and Raman) were assigned according to their distinctiveness region. The computed frequencies and optimized parameters have been calculated by using HF and DFT (B3LYP) methods and the corresponding results are tabulated. On the basis of the comparison between computed and experimental results assignments of the fundamental vibrational modes are examined. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The alternation of the vibration pattern of the pedestal molecule related to the substitutions was analyzed. The (13)C and (1)H NMR spectra have been recorded and the chemical shifts have been calculated using the gauge independent atomic orbital (GIAO) method. The Mulliken charges, UV spectral analysis and HOMO-LUMO analysis of have been calculated and reported. The molecular electrostatic potential (MEP) was constructed.

Vibrational analysis using FT-IR, FT-Raman spectra and HF-DFT methods and NBO, NLO, NMR, HOMO-LUMO, UV and electronic transitions studies on 2,2,4-trimethyl pentane.

In this work, the vibrational spectral analysis was carried out by using Raman and infrared spectroscopy in the range 100-4000cm(-1)and 50-4000cm(-1), respectively, for 2,2,4-Trimethyl Pentane, TMP (C8H18) molecule. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimizations and geometrical parameter calculations based on Hartree Fock (HF) and density functional theory (DFT) method with 6-311++G(d,p) basis set. The scaled B3LYP/6-311++G(d,p) results shows the best agreement with the experimental values over the other method. The calculated HOMO and LUMO energies shows that charge transfer within the molecule. The physical reactions of single bond hydrocarbon TMP were investigated. The results of the calculations were applied to simulate spectra of the title compound, which shows the excellent agreement with observed spectra. Besides, Mulliken atomic charges, UV, frontier molecular orbital (FMO), MEP, NLO activity, Natural Bond-Orbital (NBO) analysis, NMR and thermodynamic properties of title molecule were also performed.

Molecular structure and vibrational spectroscopic studies on 2-furanacetic acid monomer and dimer.

In this work, molecular geometries and fundamental vibrational frequencies of 2-furanacetic acid (2FAA) and its hydrogen bonded dimer were investigated using DFT/B3LYP method with 6-311++G(d,p) as basis set. The FT-infrared and FT-Raman spectra of the 2FAA compound were recorded in the region 4000-400 cm(-1). The theoretical wavenumbers were scaled and compared with experimental FT-IR and FT-Raman spectra. Complete vibrational assignments and analysis of the fundamental modes of monomer and dimer structures were performed on the basis of the potential energy distribution (PED) calculations. A study on the electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, are performed by time-dependent DFT (TD-DFT) approach. Molecular stability arising from hyperconjugative interactions and charge delocalization has been analyzed using Natural Bond Orbital (NBO) analysis. Topological parameters such an electron density and its Laplacian at bond critical points (BCP) of O-H and O⋯H contact bonds were analyzed in details with the help of the atoms in molecules (AIM) approach in order to study the intermolecular hydrogen bonding. The nonlinear optical properties of the title molecule have been investigated. Moreover, molecular electrostatic potential (MEP) surface was plotted for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The nonlinear optical properties were reported and compared with that of the urea. The thermodynamic properties like heat capacity, entropy, and enthalpy have been calculated for the molecule at different temperatures.

Spectroscopic and quantum chemical analysis of Isonicotinic acid methyl ester.

In this present study, an organic compound Isonicotinic acid methyl ester (INAME) was structurally characterized by FTIR, FT-Raman, and NMR and UV spectroscopy. The optimized geometrical parameters and energies of all different and possible conformers of INAME are obtained from Density Functional Theory (DFT) by B3LYP/6-311++G(d,p) method. There are three conformers (SI, SII-1, and SII-2) for this molecule (ground state). The most stable conformer of INAME is SI conformer. The molecular geometry and vibrational frequencies of INAME in the ground state have been calculated by using HF and density functional method (B3LYP) 6-311++G (d,p) basis set. Detailed vibrational spectral analysis has been carried out and assignments of the observed fundamental bands have been proposed on the basis of peak positions and relative intensities. The computed vibrational frequencies were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. A study on the electronic properties, such as HOMO and LUMO energies were performed by time independent DFT approach. Besides, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (µ) and first hyper polarizability (ß) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results show that the INAME molecule may have microscopic nonlinear optical (NLO) behavior with non zero values. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by gauge independent atomic orbital (GIAO) method.

Normal coordinate analysis and vibrational spectroscopy (FT-IR and FT-Raman) studies of 5-methyl-N-[4-(trifluoromethyl) phenyl]-isoxazole-4-carboxamide using density functional method.

Vibrational spectral analysis of 5-methyl-N-[4-(trifluoromethyl) phenyl]-isoxazole-4-carboxamide is (5MN4TPI4C) molecule was carried out using FT-IR and FT-Raman spectroscopic techniques. The equilibrium geometry, harmonic vibrational wavenumbers, various bonding features have been computed using density functional B3LYP method with 6-311G(d,p) as basis set. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFFM). Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The non-linear optical (NLO) behavior of 5MN4TPI4C has been studied by determination of the electric dipole moment (µ) and hyperpolarizability (ß) by using B3LYP/6-311G(d,p) method. The molecular orbital compositions and their contributions to the chemical bonding are studied by Total density of energy states (TDOS), sum of α and ß electron (αßDOS) density of states. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are calculated.

Structure and vibrational spectra of melaminium bis(trifluoroacetate) trihydrate: FT-IR, FT-Raman and quantum chemical calculations.

Melaminium bis(trifluoroacetate) trihydrate (MTFA), an organic material has been synthesized and single crystals of MTFA have been grown by the slow solvent evaporation method at room temperature. X-ray powder diffraction analysis confirms that MTFA crystal belongs to the monoclinic system with space group P2/c. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional theory (DFT) B3LYP method with 6-311G(d,p) and 6-311++G(d,p) basis sets. The X-ray diffraction data have been compared with the data of optimized molecular structure. The theoretical results show that the crystal structure can be reproduced by optimized geometry and the vibrational frequencies show good agreement with the experimental values. The nuclear magnetic resonance (NMR) chemical shift of the molecule has been calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. HOMO-LUMO, and other related molecular and electronic properties are calculated. The Mulliken and NBO charges have also been calculated and interpreted.

Vibrational frequency analysis, FT-IR, FT-Raman, ab initio, HF and DFT studies, NBO, HOMO-LUMO and electronic structure calculations on pycolinaldehyde oxime.

In this work, the vibrational spectral analysis is carried out by using Raman and infrared spectroscopy in the range 100-4000 cm(-1)and 50-4000 cm(-1), respectively, for pycolinaldehyde oxime (PAO) (C6H6N2O) molecule. 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 HF and B3LYP methods with 6-311++G(d,p) basis set. The results of the calculation shows excellent agreement between experimental and calculated frequencies in B3LYP/6-311++G(d,p) basis set. The optimized geometric parameters are compared with experimental values of PAO. The non linear optical properties, NBO analysis, thermodynamics properties and mulliken charges of the title molecule are also calculated and interpreted. A study on the electronic properties, such as HOMO and LUMO energies, are performed by time-dependent DFT (TD-DFT) approach. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) are performed. The effects due to the substitutions of CH=NOH ring are investigated. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule are calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

Vibrational, DFT, thermal and dielectric studies on 3-nitrophenol-1,3,5-triazine-2,4,6-triamine (2/1).

A new organic-organic salt, 3-nitrophenol-1,3,5-triazine-2,4,6-triamine (2/1) (3-NPM) has been synthesized by slow evaporation technique at room temperature. Single crystal X-ray diffraction analysis reveals that 3-NPM crystallizes in orthorhombic system with centrosymmetric space group Pbca and the lattice parameters are a=15.5150(6) Å, b=12.9137(6) Å, c=17.8323(6) Å, α=ß=γ=90° and V=3572.8(2)(Å)(3). The geometry, fundamental vibrational frequencies are interpreted with the aid of structure optimization and normal coordinate force field calculations based on density functional theory (DFT) B3LYP/6-311G(d,p) method. IR and Raman spectra of 3-NPM have been recorded and analyzed. The complete vibrational assignments are made on the basis of potential energy distribution (PED). The electric dipole moment, polarizability and the first order hyperpolarizability values of the 3-NPM have been calculated. (1)H and (13)C NMR chemical shifts are calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP method with 6-311G (d,p) basis set. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties are performed. Mulliken and Natural charges of the title molecule are also calculated and interpreted. Thermal decomposition behavior of 3-NPM has been studied by means of thermogravimetric analysis. The dielectric measurements on the powdered sample have been carried out and the variation of dielectric constant and dielectric loss at different frequencies of the applied field has been studied and the results are discussed in detail.

Larvicidal & ovicidal efficacy of Pithecellobium dulce (Roxb.) Benth. (Fabaceae) against Anopheles stephensi Liston & Aedes aegypti Linn. (Diptera: Culicidae).

BACKGROUND & OBJECTIVES: In view of the recently increased interest in developing plant origin insecticides as an alternative to chemical insecticide, this study was undertaken to assess the larvicidal and ovicidal potential of the crude hexane, benzene, chloroform, ethyl acetate and methanol solvent extracts from the medicinal plant Pithecellobium dulce against the mosquito vectors, Anopheles stephensi and Aedes aegypti (Diptera: Culicidae). METHODS: Larvicidal activity of P. dulce plant extracts was studied in the range of 60 to 450 mg/l against early third instar larvae of An. stephensi and Ae. aegypti in the laboratory. The larval mortality was observed after 24 h of exposure. The ovicidal activity was determined against An. stephensi and Ae. aegypti to various concentrations ranging from 100 to 750 mg/l under the laboratory conditions. Mean per cent hatchability of the eggs were observed after 48 h post treatment. RESULTS: All leaf and seed extracts showed moderate larvicidal and ovicidal effects; however, the highest larval mortality was found in methanol extract of leaf of P. dulce against the larvae of An. stephensi and Ae. aegypti with the LC50 and LC90 values 145.43, 155.78 mg/l and 251.23, 279.73 mg/l, respectively. The per cent hatchability was inversely proportional to the concentration of extract and directly proportional to the eggs. Zero hatchability was observed at 400 mg/l for leaf methanol extract and 625 mg/l for seed methanol extract of P. dulce against An. stephensi and Ae. aegypti, respectively. Compared to leaf extracts, seed extracts have low potency against the two mosquitoes. INTERPRETATION & CONCLUSIONS: The present results suggest that the leaf and seed extracts of P. dulce have the potential to be used as an ideal eco-friendly approach for the control of mosquitoes.

Chemical composition and larvicidal activity of essential oil from Ocimum basilicum (L.) against Culex tritaeniorhynchus, Aedes albopictus and Anopheles subpictus (Diptera: Culicidae).

The toxicity of mosquito larvicidal activity of leaf essential oil and their major chemical constituents from Ocimum basilicum were evaluated against Culex tritaeniorhynchus, Aedes albopictus and Anopheles subpictus. The chemical composition of the leaf essential oil was analyzed using gas chromatography-mass spectroscopy. GC-MS revealed that the essential oil of O. basilicum contained 20 compounds. The major chemical components identified were linalool (52.42%), methyl eugenol (18.74%) and 1, 8-cineol (5.61%). The essential oil had a significant toxic effect against late third-stage larvae of Cx. tritaeniorhynchus, Ae. albopictus and An. subpictus with an LC(50) values of 14.01, 11.97 and 9.75 ppm and an LC(90) values of 23.44, 21.17 and 18.56 ppm, respectively. The results could be useful in search for newer, safer, and more effective natural larvicidal agents against Cx. tritaeniorhynchus, Ae. albopictus and An. subpictus.

FT-IR, FT-Raman and UV spectral investigation: computed frequency estimation analysis and electronic structure calculations on 1-bromo-2-methylnaphthalene.

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 1-bromo-2-methylnaphthalene (C11H9Br) 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 with different basis sets combinations. 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 vibrational 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. In addition, molecular electrostatic potential and nonlinear optical and thermodynamic properties of the title compound were performed. Mulliken charges and NBOs of the title molecule were also calculated and interpreted.

Seckel syndrome: a report of a case.

Seckel syndrome, first defined by Seckel in 1960, is a rare (incidence 1:10,000), genetically heterogeneous autosomal recessive disorder presenting at birth. This syndrome is characterized by a proportionate dwarfism of prenatal onset, a severe microcephaly with a "bird-headed" like appearance (beaked nose, receding forehead, prominent eyes, and micrognathia), and mental retardation. The significance of dental alterations in this syndrome resides in the defect, hypoplastic enamel, being limited to the primary dentition; in most instances the second primary molar tooth is not affected. A case of the Seckel syndrome is presented.

Adulticidal properties of Cardiospermum halicacabum plant extracts against three important vector mosquitoes.

OBJECTIVE: To determine adulticidal activitiy of hexane, ethyl acetate, benzene, chloroform and methanol leaf extracts of Cardiospermum halicacabum against Culex quinquefasciatus (Cx. quinquefasciatus), Aedes aegypti (Ae. aegypti) and Anopheles stephensi (An. stephensi). MATERIALS AND METHODS: The bioassay was conducted in an experimental kit consisting of two cylindrical plastic tubes both measuring 125 x 44 mm following the WHO method; Mortality of the mosquitoes was recorded after 24 h. RESULTS: The adulticidal activity of plant extracts showed moderate toxic effect on the adult mosquitoes after 24 h of exposure period. However, compared to other solvents highest mortality was found in methanol extract of C. halicacabum against all the three mosquitoes. Among them An. stephensi produce the highest LC50 and LC90 (186.00 and 346.06 ppm) values. CONCLUSIONS: From the results it can be concluded the crude extract of C. halicacabum was an excellent potential for controlling Cx. quinquefasciatus, Ae. aegypti and An. stephensi mosquitoes.

FT-IR and FT-Raman spectra, thermo dynamical behavior, HOMO and LUMO, UV, NLO properties, computed frequency estimation analysis and electronic structure calculations on α-bromotoluene.

In this work, the vibrational spectral analysis was carried out by using Raman and infrared spectroscopy in the range 100-4,000 cm(-1) and 50-4,000 cm(-1), respectively, for the title molecules. 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 Hartee Fock (HF) and density functional theory (DFT) method and different basis sets combination. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The scaled B3LYP/6-311++G(d,p) results show the best agreement with the experimental values over the other methods. The calculated HOMO and LUMO energies show that charge transfer occurs within molecule. The influences of bromine atom and methyl group on the geometry of benzene and its normal modes of vibrations have also been discussed. The results of the calculations were applied to simulated spectra of the title compounds, which show excellent agreement with observed spectra.

Spectroscopic (FT-IR, FT-Raman, UV and NMR) investigation and NLO, HOMO-LUMO, NBO analysis of organic 2,4,5-trichloroaniline.

In this work, the experimental and theoretical study on the molecular structure and vibrational spectra of 2,4,5-trichloroaniline (C(6)H(4)NCl(3), abbreviated as 2,4,5-TClA) were studied. The FT-IR and FT-Raman spectra were recorded. The molecular geometry and vibrational frequencies in the ground state were calculated by using the Hartree-Fock (HF) and density functional theory (DFT) methods (B3LYP) with 6-311++G(d,p) basis set. Comparison of the observed fundamental vibrational frequencies of 2,4,5-TClA with calculated results by HF and DFT indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. Besides, molecular electrostatic potential (MEP) and thermodynamic properties were performed. The electric dipole moment (µ) and the first hyperpolarizability (ß) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 2,4,5-TClA molecule may have microscopic nonlinear optical (NLO) behavior with non-zero values. Mulliken atomic charges of 2,4,5-TClA was calculated and compared with aniline and chlorobenzene molecules. The (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

Spectroscopic properties, NLO, HOMO-LUMO and NBO analysis of 2,5-Lutidine.

In this work, FT-IR and FT-Raman spectra of 2,5-Lutidine (C(7)H(9)N) have been reported in the regions 4000-400 cm(-1) and 3500-100 cm(-1), respectively. Density functional theory (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 HF and B3LYP methods with 6-311++G(d,p) basis set. The complete vibrational assignments of wavenumbers have been made on the basis of potential energy distribution (PED). The results of the calculation shows excellent agreement between experimental and calculated frequencies in B3LYP/6-311++G(d,p) basis set. The optimized geometric parameters were compared with experimental values of 2,5-Lutidine. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. Besides, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed. Mulliken charges and NBOs of the title molecule were also calculated and interpreted. The (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. The dipole moment, linear polarizability and first hyperpolarizability values were also computed.

Vibrational spectroscopic studies, NLO, HOMO-LUMO and electronic structure calculations of α,α,α-trichlorotoluene using HF and DFT.

FT-IR and FT-Raman spectra of α,α,α-trichlorotoluene have been recorded and analyzed. The geometry, fundamental vibrational frequencies are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) B3LYP/6-311++G(d,p) method and a comparative study between HF level and various basis sets combination. The fundamental vibrational wavenumbers as well as their intensities were calculated and a good agreement between observed and scaled calculated wavenumbers has been achieved. The complete vibrational assignments of wavenumbers are made on the basis of potential energy distribution (PED). The effects due to the substitutions of methyl group and halogen were investigated. The absorption energy and oscillator strength are calculated by time-dependent density functional theory (TD-DFT). The electric dipole moment, polarizability and the first hyperpolarizability values of the α,α,α-trichlorotoluene have been calculated. (1)H NMR chemical shifts were calculated by using the gauge independent atomic orbital (GIAO) method with HF and B3LYP methods with 6-311++G(d,p) basis set. Moreover, molecular electrostatic potential (MEP) and thermodynamic properties were performed. Mulliken and natural charges of the title molecule were also calculated and interpreted.