FT‐Raman and FT‐IR spectral and quantum chemical studies on some flavonoid derivatives: Baicalein and Naringenin

In this study, the experimental and theoretical results on the molecular structures of some flavonoid derivatives (Baicalein and Naringenin) are presented. The FT‐IR and FT‐Raman spectra of the compounds have been recorded together for the first time between 4000–400 cm⁻¹ and 3500–5 cm⁻¹ regions, respectively. The molecular geometry and vibrational wavenumbers of the compounds have been also calculated in their ground states by using ab initio HF and DFT/B3LYP functional with 6‐31G(d,p) basis set used in calculations. The calculations were utilized to the C₁ symmetries of the molecules. All calculations were performed with Gaussian 98 software. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. Scale factors have been used in order to compare how the calculated and experimental data are in agreement. Theoretical infrared intensities were also reported. Copyright © 2008 John Wiley & Sons, Ltd.     

Density functional theory calculation and vibrational spectral analysis of 4‐hydroxy‐3‐(3‐oxo‐1‐phenylbutyl)‐2H‐1‐benzopyran‐2‐one

The Fourier transform infrared (4000–400 cm⁻¹) and Fourier transform Raman (3500–500 cm⁻¹) spectra of 4‐hydroxy‐3‐(3‐oxo‐1‐phenylbutyl)‐2H‐1‐benzopyran‐2‐one (Warfarin) have been measured and calculated. The structure optimization has been made using density functional theory (DFT) calculations. Complete vibrational assignments of the observed spectra have been compared with theoretical wavenumbers. The wavenumber increasing in the methyl group shows the electronic hyperconjugation effect. The natural bond orbital (NBO) analysis reveals the hyperconjugation interaction and the intramolecular hydrogen bonding. The first‐order hyperpolarizability has been calculated. Copyright © 2009 John Wiley & Sons, Ltd.     

FT‐Raman,FT‐IR spectral and DFT studies on 6, 8‐dichloroflavone and 6, 8‐dibromoflavone

In this study, experimental and theoretical vibrational spectral results of the molecular structures of 6,8‐dichloroflavone (6,8‐dcf) and 6,8‐dibromoflavone (6,8‐dbf) are presented. The FT‐IR and FT‐Raman spectra of the compounds have been recorded together between 4000 and 400 cm⁻¹ and 3500–5 cm⁻¹ regions, respectively. The molecular geometry and vibrational wavenumbers of 6,8‐dcf and 6,8‐dbf in their ground state have been calculated by using DFT/B3LYP functional, with 6‐31 + + G(d,p) basis set used in calculations. All calculations were performed with Gaussian03 software. The obtained vibrational wavenumbers and optimized geometric parameters were seen to be in good agreement with the experimental data. Scale factors have been used in order to compare how the calculated and experimental data are in agreement. Theoretical infrared intensities are also reported. Copyright © 2009 John Wiley & Sons, Ltd.     

DFT,FT‐Raman,FT‐IR and NMR studies of 2‐fluorophenylboronic acid

The experimental and theoretical vibrational spectra of 2‐fluorophenylboronic acid (2fpba) were studied. The Fourier transform Raman and Fourier transform infrared spectra of the 2fpba molecule were recorded in the solid phase. The structural and spectroscopic analysis of the molecule was carried out by using Hartree‐Fock and density functional harmonic calculations. For the title molecule, only one form was found to be the most stable structure, by using B3LYP level with the 6‐31++G(d,p) basis set. Selected experimental bands were assigned and characterized on the basis of the scaled theoretical wavenumbers by their total energy distribution (TED). The ¹H and ¹³C nuclear magnetic resonance (NMR) chemical shifts of the 2fpba molecule were calculated using the Gauge‐Invariant‐ atomic orbital (GIAO) method in DMSO solution using IEF‐PCM model and compared with the experimental data. Finally, geometric parameters, vibrational wavenumbers and chemical shifts were compared with available experimental data of the molecule. Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular structure,spectroscopic (FTIR,FTIR gas phase,FT‐Raman) first‐order hyperpolarizability and HOMO–LUMO analysis of 4‐methoxy‐2‐methyl benzoic acid

Vibrational spectral analysis was carried out for 4‐methoxy‐2‐methyl benzoic acid (4M2MBA) by using Fourier transform infrared (FT‐IR) (solid, gas phase) and FT‐Raman spectroscopy in the range of 400–4000 and 10–3500 cm⁻¹ respectively. The effects of molecular association through O H···O hydrogen bonding have been described by the single dimer structure. The theoretical computational density functional theory (DFT) and Hatree‐Fock (HF) method were performed at 6–311++G(d,p) levels to derive the equilibrium geometry, vibrational wavenumbers, infrared intensities and Raman scattering activities. The scaled theoretical wavenumbers were also shown to be in good agreement with experimental data. The first‐order hyperpolarizability (β₀) of this novel molecular system and related properties (β, α₀ and Δα) of 4M2MBA are calculated using the B3LYP/cc‐pvdz basis set, based on the finite‐field approach. A detailed interpretation of the infrared and Raman spectra of 4M2MBA is reported. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule were also constructed and compared with the experimental one. Copyright © 2010 John Wiley & Sons, Ltd.     

Density functional theory calculations and vibrational spectra of p‐bromonitrobenzene

FT‐IR and FT‐Raman spectra of p‐bromonitrobenzene (p‐BNB) have been recorded in the region 4000–400 cm⁻¹ and 4000–50 cm⁻¹, respectively. The molecular structure, geometry optimization, vibrational wavenumbers have been investigated. The spectra were interpreted with the aid of normal coordinate analysis based on the density functional theory (DFT) using the standard B3LYP/6‐31G method and basis set combination and was scaled using multiple scale factors yielding good agreement between observed and calculated wavenumbers. The results of the calculations are applied to simulate infrared and Raman spectra of the title compound which showed reasonable agreement with the observed spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Spectral and Computational Studies on Benzil Mono-(2-Pyridyl)Hydrazone

In the present study, structural properties of Mono-(2-Pyridyl) Hydrazone were studied extensively utilizing density functional theory (DFT) employing B3LYP exchange correlation. The Fourier transform infrared (solid phase) was recorded. The vibrational frequencies in the ground state were calculated by using density functional method (B3LYP) with 6-31G* and 6-311G** as basis sets. The spectral studies revealed that the title compound exists in Keto form. Spectral techniques that we employed include ¹H and ¹³C NMR, electronic, thermal techniques. Correlation between experimental chemical shifts and GIAO/B3LYP/6-311G**-calculated isotropic shielding constants, δ_exp = a + bσ_calc, are reported. Good linear regressions between experimental and theoretical results for ¹H and ¹³C were obtained.     

Vibrational properties of polysiloxanes: from dimer to oligomers and polymers. 1. Structural and vibrational properties of hexamethyldisiloxane (CH3)3SiOSi(CH3)3

The hexamethyldisiloxane (HMDS)(CH₃)₃SiOSi(CH₃)₃ molecule is one of the basic building blocks of silicones and polysiloxanes, as it is used for many chain terminations. Far‐infrared, mid‐infrared, and polarized Raman spectroscopic studies, combined with quantum chemical calculations and vibrational normal mode analyses, were performed for the HMDS molecule. The internal rotation of the trimethylsilyl group was calculated to be nearly free. The large‐amplitude bending motion was found very anharmonic with a barrier to linearity below 4 kJ/mol. Exhaustive assignments of observed wavenumbers have been performed on the basis of calculated potential energy distributions (PED) and atomic displacements. By isotopic ¹⁶O ¹⁸O substitution, the Si O Si symmetric and antisymmetric stretching modes shift from 521 and 1074 cm⁻¹ to 514 and 1028 cm⁻¹, respectively. This spectroscopic observation provides convincing evidence that the molecule is bent with an angle estimated at around 150°. The comparison of HMDS vibrational spectra with the vibrational spectra of some siloxane derivatives reveals strong effects of silicon substituents on the Si O Si symmetric and antisymmetric stretchings. The Si O Si siloxane bridge group plays a key role in the properties of the HMDS molecule and may also account for some important silicone polymer properties such as their very low glass transition, their high compressibility, and their low surface tension. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational properties of graphene and graphene layers

The phonon dispersions of graphene and graphene layers are theoretically investigated within fifth‐nearest‐neighbor force‐constant approach. Based on their symmetry groups, the number of Raman‐ and infrared‐active modes at the Γ point is given. Interatomic force constants are recalculated by fitting them to experimental phonon energy dispersion curves. Wavenumbers of optically active modes are presented as a function of number of layers (n). Our calculated results reproduce well the experimental data of G peak for graphene (1587 cm⁻¹) and graphite (1581.6 cm⁻¹) and clearly give the relation that ω_G = 1581.6 + 11/(1 + n^1.6). Copyright © 2009 John Wiley & Sons, Ltd.     

Infrared and Raman Spectra of bis-Thiourea Lead(II) Chloride

Abstract

PbCl₂.2[(SC(NH₂)₂] is an important complex for environmental chemistry. Single crystals were studied using infrared absorption, and Raman spectroscopy in low temperature conditions (10 K). Assignments of the lead complex bands were made by searching correlations and group frequencies with separate PbCl₂ and thiourea spectra in the solid state. Lattice modes separation was achieved down to 20 cm^?1 in Raman and down to 50 cm^?1 with far infrared spectroscopy. Spectral signatures of the unusual seven-coordinated lead in the complex were tentatively determined and are in accordance with structural data.

     

High-Resolution Infrared Study of PHD2: The P-H Stretching Bands ν1 and 2ν1

For the first time the infrared spectrum of PHD₂ was recorded in the region of the PH stretching fundamental ν₁ at 2324.005 cm⁻¹ and the overtone 2ν₁ at 4563.634 cm⁻¹ with a resolution of 4.2×10⁻³ cm⁻¹ and 8.8×10⁻³ cm⁻¹, respectively. In the analyses about 1340 and 1020 transitions were assigned to the corresponding ν₁ and 2ν₁ bands, which provided 316 and 248 upper energies, respectively. Since both the bands are sufficiently isolated, a standard Watson-type Hamiltonian (A-reduction, I^r-representation) was employed. The obtained sets of spectroscopic parameters correlate very well both with each other, and with the corresponding parameters of the ground vibrational state.     

Comparison Between the IR Spectra and the Structure of the Two Conformations of a Diazabicyclanol

Abstract

In the two stable conformations of the diazabicyclanol 3, 7-dimethyl-3, 7-diazabicyclo[3. 3. 1]nonan-9-ol, chair-chair (Va) and chair-boat (Vb), the infrared spectra (200–4000 cm^?1) were recorded, compared and their vibrations analysed. Using the AMI senlempirical method, the geometry was fully optimized in both forms, and the theoretical Infrared spectra were calculated and compared. In the (Vb) conformation, the IR spectra were recorded in CCl₃D, CCl₄ and S₂C solvents. Some correlations were established.     

Coupling of the Double Bond Stretching Vibration in Divinyl Ethers

Abstract

Examination of the Infrare and Raman spectra of cis, cis-dipropenyl ether (which was produced by isomerization of diallyl ether) has produced evidence for strong vibrational coupling between the two double-bonds. This ether has strong bands it 1655 cm^?1 in the infrared and at 1691 cm^?1 in the Raman. The 1658 cm^?1 band in the Raman is about 10 fold less intense than the strong polarised band. Thus it appears reasonable to associate the strong IR and Raman bands with the asymmetric and symmetric vibrations shown.     

Infrared and near infrared emission spectra of SbH and SbD

The X³Σ⁻ ground state vibration-rotation spectrum of SbH and the near infrared spectra of the b¹Σ⁺-X³Σ⁻ transitions of SbH and SbD have been measured at high resolution by Fourier transform spectroscopy. The SbH and SbD radicals were generated in a tube furnace with a D.C. discharge of a flowing mixture of argon, hydrogen (or deuterium), and antimony vapor. In the infrared region, the 1-0 and 2-1 bands of the three components (0⁺, 1_e, and 1_f) as well as the 0⁺ component of the 3-2 band were observed for ¹²¹SbH and ¹²³SbH. In the near infrared region, the 0-0, 1-1, and 2-2 bands of the b¹Σ⁺-X³Σ⁻ system of both SbH and SbD as well as the 3-3 band of SbD were observed. Except for a few lines, the antimony isotopic shift was not resolved for these electronic spectra. The present data set was combined with the available ground state data on SbD and a¹Δ data for SbH and SbD from previous work, and a least-squares fit was performed for each of the four isotopologues: ¹²¹SbH, ¹²³SbH, ¹²¹SbD, and ¹²³SbD. Improved spectroscopic constants were obtained for the observed vibrational levels of the X³Σ⁻, a¹Δ, and b¹Σ⁺ states of these four isotopologues. In addition, all the above data were also fitted simultaneously to a multi-isotopologue Dunham model, which yielded Dunham constants and Born-Oppenheimer breakdown parameters for these three electronic states. Interestingly, we found that Born-Oppenheimer breakdown corrections were also required for some of the spin-spin and spin-rotation parameters of the X³Σ⁻ state.     

The Enfrared Spectra of tris (Methyl Methylphosphonate) Iron(III), Tris (Ethyl Ethylphosphonate) Iron(III), and Tris (Isopropyl Methylphosphonate) Iron(III)

The literature contains few references to the reactions of phosphonate esters with iron salts. Guilbault et al. ¹ recently studied the infrared spectrs of diisopropyl methylphosphonate (DIMP) and dimethyl methylphosphonate (DIMP) chemisorbed on solid FeCl ³ and made infrared band assignments. We wish to report the results of a study of the products of the homogeneous reaction of DIMP, DMMP and diethyl ethylphosphonate (DEEP) with ferric chloride. On the basis of elemental analysis and infrared absorption data, the products isolated were identified as tris (methylmethylphosphonate) iron (III), tris (ethyl ethylphosphonate) iron (III), and tris (isopropyl methylphosphonate) iron (III).     

FT‐Raman,FT‐IR spectra and DFT calculations on monomeric and dimeric structures of 5‐fluoro‐ and 5‐chloro‐salicylic acid

The experimental and theoretical study on the structures and vibrations of 5‐fluoro‐salicylic acid and 5‐chloro‐salicylic acid (5‐FSA and 5‐ClSA, C₇H₅FO₃ and C₇H₅ClO₃) is presented. The Fourier transform infrared spectra (4000–400 cm⁻¹) and the Fourier transform Raman spectra (4000–50 cm⁻¹) of the title molecules in the solid phase were recorded. The molecular structures, vibrational wavenumbers, infrared intensities, Raman intensities and Raman scattering activities were calculated for a pair of molecules linked by the intermolecular O H···O hydrogen bond. The geometrical parameters and energies of 5‐FSA and 5ClSA were obtained for all eight conformers/isomers from density functional theory (DFT) (B3LYP) with 6‐311++G(d,p) basis set calculations. The computational results identified the most stable conformer of 5‐FSA and 5‐ClSA 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. The spectroscopic and theoretical results were compared with the corresponding properties for 5‐FSA and 5‐ClSA monomers and dimer of C1 conformer. The optimized bond lengths, bond angles and calculated wavenumbers showed the best agreement with the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

Total FTIR Spectra Translation for Improving Quantification of Protids

Abstract

In infrared spectroscopy, uncertain variations of the baseline are observed and these add an arbitrary constant to every absorbance. We have recently proposed an automatic baseline correction method by total translation of the infrared spectrum with regard to a reference spectrum (Cadet and Offmann, 1996a). This method improved the precision of the values obtained during quantitative determination of parotids in raw sugar cane juices: the mean and standard deviation values before correction were 1.3 × 10^?2 and 8.58 × 10^?2 and after correction they were 1.4 × 10^?2 and 7.05 × 10^?2respectively.     

Experimental vibrational spectra (Raman,infrared) and DFT calculations on monomeric and dimeric structures of 2‐ and 6‐bromonicotinic acid

In this work, the Fourier transform infrared and Raman spectra of 2‐bromonicotinic acid and 6‐bromonicotinic acid (abbreviated as 2‐BrNA and 6‐BrNA, C₆H₄BrNO₂) have been recorded in the region 4000–400 and 3500–50 cm⁻¹. The optimum molecular geometry, normal mode wavenumbers, infrared intensities and Raman scattering activities, corresponding vibrational assignments and intermolecular hydrogen bonds were investigated with the help of B3LYP density functional theory (DFT) method using 6‐311++G(d,p) basis set. Reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated with scaled quantum mechanical (SQM) method. From the calculations, the molecules are predicted to exist predominantly as the C1 conformer. Copyright © 2009 John Wiley & Sons, Ltd.     

A theoretical spectroscopic study of single ammonia molecules adsorbed on the surface of fcc-type argon clusters. Surface effects on the ν 2 vibration-inversion mode

Ammonia monomers have been adsorbed on argon clusters at low temperature K by Rohmund and Huisken [#!frfh97!#] using the pick-up technique. They measured the spectrum of the NH₃ molecules in the region of the umbrella mode. Two broad bands centered around 970 and 1000 cm^-1 with finer details were observed. The authors attempted to interpret the obtained spectrum on the basis of the free rotation motions of the molecules. In this paper semi-empirical atom-atom potential energy calculations are performed for the ammonia monomer adsorbed on a rigid face-centered-cubic (fcc)-type surface of the argon cluster. In the equilibrium position of the rigid molecule on the cluster surface the orientational potential energy surface exhibits two quasi-equivalent minima separated by a potential barrier of about 100 cm^-1. The symmetry of the molecular vibration-inversion double-well potential is destroyed; the inversion motion is then forbidden in the ground state. On the basis of the two adsorption orientations, the vibrational frequency shifts are calculated and the obtained infrared bar-spectrum agrees with the experimental one. Received 6 April 1999 and Received in final form 19 July 1999     

A Spectroscopic Study of Polynuclear Complex of Iron(III) with Inuline Oligomers

The infrared spectra of the hydrates of inuline oligomers and the complex of iron(III) with inuline oligomers and their partial deuterated analogs were studied. From the appearance and frequencies of the bands in the range of OH and OD vibrations it was concluded that these crystalohydrates have one type of H₂O molecule, and relatively weak hydrogen bond (estimated O_w…O distances are 280 and 283 pm for inuline and its complex, respectively). From the FTIR spectra of the complex the β₂-form for iron(III) oxihydroxide (FeOOH) was determined. On the basis of the electron spin resonance spectra it was concluded that Fe⁺³ ions of octahedral configuration (g-value 2.03 ± 0.01) were present in the complex. From the measured ESR line width (ΔH = 100 ± 5 mT) the approximate Fe inter atomic distance of 0.21 nm was calculated, indicating a dense packing of Fe atoms in the cluster.