Vibrational assignments of 2-iodopyridine

A review of the vibrational assignments for 2-iodopyridine has been proposed based on the FT-Raman (3500-50cm(-1)) and IR (4000-400cm(-1)) spectral measurements. Equilibrium geometries and vibrational frequencies have been computed from a variety of electronic structure methods: the ab initio (RHF), six DFT (BLYP, BP86, B3LYP, B3P86, B3PW91 and SVWN) and MP2 methods using 3-21G*, LANL2DZ and DGDZVP basis sets. A normal coordinate analysis has been carried out: the normal modes and their couplings are characterized in terms of potential energy distributions (PEDs). The comparison of assignments for pyridine and halopyridines shows that several of the normal modes arise from coupled vibrations in 2-iodopyridine. The BP86 and B3LYP methods with LANL2DZ basis set have performed reasonably well in reproducing the observed spectra, demonstrating that the LANL2DZ basis set (with effective core potential representations of electrons near the nuclei for post-third row atoms) is suitable for 2-iodopyridine.     

Vibrational assignments and electronic structure calculations for 3-acetylcoumarin

Laser Raman (3500-50 cm(-1)) and IR (4000-400 cm(-1)) spectral measurements have been made on the laboratory prepared solid 3-acetylcoumarin. Molecular electronic energy, equilibrium geometrical structure and harmonic vibrational spectra have been computed at the RHF/6-31G(d,p) and B3LYP/6-31G(d,p) levels of theory. A complete vibrational assignment aided by the theoretical harmonic frequency analysis has been proposed. The B3LYP/6-31G(d,p) geometrical parameters, and frequencies of the C=O in the pyrone and acetyl group are in good agreement with experiment. The difference in the frequencies due to the two carbonyl groups, 50 cm(-1), which is attributed to the conjugation effect, is accounted for by the B3LYP to be 56cm(-1).     

FT-Raman and infrared spectra and vibrational assignments for 3-chloro-4-methoxybenzaldehyde, as supported by ab initio, hybrid density functional theory and normal coordinate calculations

Fourier-transform laser Raman (3500-50 cm(-1)) and infrared (4000-400 cm(-1)) spectral measurements have been made for the solid 3-chloro-4-methoxybenzaldehyde. The electronic structure calculations -ab initio (RHF) and hybrid density functional methods (B3LYP and B3PW91) -- have been performed with 6-31G* and 6-311G* basis sets. Molecular electronic energies, equilibrium geometries, IR and Raman spectra have been computed. Potential energy distribution (PEDs) and normal mode analysis have also been performed. A complete assignment of the observed spectra has been proposed. Investigation of the relative orientation of the aldehydic oxygen and chlorine atom with respect to the methoxy group has shown that two forms, O-cis and O-trans exist, with O-trans form being more stable. The energy difference between O-cis and O-trans forms is 0.057 kcal/mol (21 cm(-1)) with B3LYP/6-31G*, which is less than the calculated torsional vibrational frequencies of the aldehyde and methoxy group. In the CH (O) aldehydic stretching region five observed bands are probably due to multiplet Fermi resonance. An infrared doublet near 1700 cm(-1) with nearly equal intensities has been ascribed to the Fermi resonance: the two bands at 1696 and 1679 cm(-1) arise due to the interaction between the CO stretching fundamental and a combination of O-CH(3) and CC stretching vibrations.     

Experimental and computational studies of the structure and vibrational spectra of aminomethyl-dimethyl-phosphine oxide and its 15N labeled isomer

Infrared (4000-100 cm(-1)) spectra of aminomethyl-dimethyl-phosphine oxide and 15N-aminomethyl-dimethyl-phosphine oxide have been measured. Geometric parameters (bond distances and angles), net electronic charges and vibrational spectroscopic data of both compounds calculated at various levels of theory (B3LYP/6-31G* and Moeller-Plesset perturbational theory (MP2)/6-31G*) are reported. The theoretical spectral results are discussed mainly in terms of comparison with infrared (4000-100 cm(-1)) spectral data. Better coincidence was achieved with the frequencies calculated at the MP2/6-31G* level: the standard deviation is 16 cm(-1). The calculated isotopic frequency shifts, induced by the 15N labeling, are in good accordance with the measured ones. Complete vibrational assignment is made with the help of MP2 force field calculations. Data obtained here are used to reassign some of the vibrational frequencies.     

Conformational stability, vibrational assignmenents, barriers to internal rotations and ab initio calculations of 2-aminophenol (d 0 and d3)

The Raman (3700-100 cm(-1)) and infrared (4000-400 cm(-1)) spectra of solid 2-aminophenol (2AP) have been recorded. The internal rotation of both OH and NH2 moieties produce ten conformers with either Cs or C1 symmetry. However, the calculated energies as well as the imaginary vibrational frequencies reduce rotational isomerism to five isomers. The molecular geometry has been optimized without any constraints using RHF, MP2 and B3LYP levels of theory at 6-31G(d), 6-311+G(d) and 6-31++G(d,p) basis sets. All calculations predict 1 (cis; OH is directed towards NH2) to be the most stable conformation except RHF/6-31++G(d,p) basis set. The 1 (cis) isomer is found to be more stable than 8 (trans; OH is away from the NH2 moiety and the NH bonds are out-of-plane) by 1.7 kcal/mol (598 cm(-1)) as obtained from MP2/6-31G(d) calculations. Aided by experimental and theoretical vibrational spectra, cis and trans 2AP are coexist in solution but cis isomer is more likely present in the crystalline state. Aided by MP2 and B3LYP frequency calculations, molecular force fields, simulated vibrational spectra utilizing 6-31G(d) basis set as well as normal coordinate analysis, complete vibrational assignments for HOC6H4NH2 and DOC6H4ND2 have been proposed. Furthermore, we carried out potential surface scan, to determine the barriers to internal rotations of NH2 and OH groups. All results are reported herein and compared with similar molecules when appropriate.     

Infrared and Raman spectra, conformational stability, ab initio calculations and vibrational assignments for trans-3-chloropropenoyl chloride

The infrared (3500-30 cm(-1)) spectra of gaseous and solid and the Raman (3500-200 cm(-1)) spectra of the liquid with quantitative depolarization ratios and solid trans-3-chloropropenoyl chloride (trans-ClCHCHCClO) have been recorded. These data indicate that both the anti (carbonyl bond trans to the carbon-carbon double bond) and syn conformers are present in the fluid states but only the anti conformer is present in the crystalline state. The mid-infrared spectra of the sample dissolved in liquid xenon as a function of temperature (-55 to -100 degrees C) have been recorded. Utilizing conformer pairs at 870 and 725 cm(-1), 1215 and 1029 cm(-1), and 1215 and 1228 cm(-1), the enthalpy difference has been determined to be 136+/-5 cm(-1) (389+/-14 cal mol(-1)) with the anti conformer the more stable form. Optimized geometries and conformational stabilities were obtained from ab initio calculations at the levels of RHF/6-31G(d), MP2/6-31G(d), MP2/6-311 + + G(d,p), MP2/6-311 + + G(2d,2p) and MP2/6-311 + + G(2df,2pd) with only the latter two calculations predicting the anti rotamer to be the more stable form. The vibrational frequencies, harmonic force constants and infrared intensities were obtained from the MP2/6-31G(d) calculations, whereas the Raman activities and depolarization values were obtained from the RHF/6-31G(d) calculations. The spectra are interpreted in detail and the results are compared with those obtained for some related molecules.     

Vibrational spectra and structure of benzil and its 18O- and d10-labelled derivatives: a quantum chemical and experimental study

Geometry and vibrational spectroscopic data of benzil-d0 benzil-d10 and benzil-18O calculated at various levels of theory (RHF/6-31G*, B3LYP/6-31G*, BLYP/6-31G*) are reported. The theoretical results are discussed mainly in terms of the comparisons with infrared (4000-100 cm(-1)) and Raman (4000-50 cm(-1)) spectral data. The calculated isotopic frequency shifts, induced by the 18O- and d10-labeling, are in a good agreement with the measured values. A complete vibrational assignment was made with the help of ab initio force field calculations. The data thus obtained were used for reassigning some vibrational frequencies. The results of the optimized molecular structure obtained on the basis of RHF and the DFT calculations are presented and compared with the experimental X-ray diffraction for the benzil-d0 single crystal. It turns out that the best structural parameters are predicted by the B3LYP/6-31G* method.     

The vibrational spectra, assignments and ab initio/DFT analysis for 3-chloro, 4-chloro and 5-chloro-2-methylphenyl isocyanates

The Raman (3500-50 cm(-1)) and infrared (4000-200 cm(-1)) spectra of 3-chloro, 4-chloro and 5-chloro-2-methylphenyl isocyanates have been measured. Ab initio and density functional theory calculations, at the levels of RHF/6-311G* and B3LYP/6-311G*, have been performed: energies, optimized geometrical parameters, vibrational frequencies, infrared intensities, Raman activities, depolarization ratios and nuclear displacements are obtained. Potential energy distributions (PEDs) and normal modes, for the spectral data computed at B3LYP/6-311G*, have also been obtained from a force-field calculations. A complete vibrational assignments of the observed spectra have been proposed. The force-field calculations have shown that, several of the normal modes are coupled, as is the case with large molecular systems possessing very low or no symmetry, such as investigated in the present study. Further, the investigation of the internal rotation of the isocyanate, NCO, by B3LYP/6-31G* level of theory has shown that the moiety maintains nearly the same orientation in all the three compounds (approximately 140-145 degrees tilt to the para-position) as in phenyl isocyanate. Two conformers, cis and trans forms, with respect to the substituents, NCO and CH(3), have been determined: the cis form lies above trans form by less than a kilocalorie per mole for each compound.     

Fourier transform-infrared and Raman spectra, ab initio calculations and assignments for 6-methyl-4-bromomethylcoumarin

Fourier transform-infrared (4000-400 cm-1) and Raman (3500-50 cm-1) spectral measurements have been made for 6-methyl-4-bromomethylcoumarin. Equilibrium structures, harmonic vibrational frequencies, infrared intensities, and depolarization ratios have been computed at RHF/6-31G* and B3LYP/6-31G* levels of theory. Twisting CH2Br moiety in the geometry optimization leads to the most stable conformer lacking symmetry (C1). This is reflected in the richness of bands in the experimental spectra. A complete assignments of the bands, aided by the ab initio calculations, has been proposed for the 6-methyl-4-bromomethylcoumarin. Due to lack of symmetry, several normal vibrations have been found to be mixed ones.     

Vibrational assignments for 7-methyl-4-bromomethylcoumarin, as aided by RHF and B3LYP/6-31G* calculations

Infrared (4000-400 cm(-1)) and Raman (3500-50 cm(-1)) spectral measurements have been made for the solid sample of 7-methyl-4-bromomethylcoumarin. Electronic structure calculations at RHF/6-31G* and B3LYP/6-31G* levels of theory have been performed, giving equilibrium geometries, harmonic vibrational spectra and normal modes. Different orientations of bromomethyl group have yielded only two conformers, of which the most stable one lying lower from the other conformer by approximately 7.99 kJ/mol, is non-planar with no symmetry. A complete assignment of the vibrational modes, aided by the calculations, has been proposed. Coupled vibrations are manifest in many modes. Some spectral features, compared to 6-methyl-4-bromomethylcoumarin, show changes across both IR and Raman spectra, involving mainly skeletal vibrations, and to a lesser degree, methyl and bromomethyl vibrations. Low-frequency vibrations below 150 cm(-1) are assigned to lattice modes.     

Conformational stability of CH3CH2PH2BH3 from temperature dependent FT-IR spectra of xenon solutions and r0 structural parameters

Variable temperature (-55--100 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylphosphine-borane, CH3CH2PH2BH3, and ethylphosphine-borane-d5 dissolved in liquid xenon have been recorded. From these data, the enthalpy difference has been determined to be 86 +/- 8 cm(-1) (1.03 +/- 0.10 kJ/mol), with the trans conformer the more stable rotamer. Complete vibrational assignments are presented for both conformers, which are consistent with the predicted frequencies obtained from the ab initio MP2/6-31G(d) calculations. The optimized geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, and depolarization ratios have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations. These quantities are compared to the corresponding experimental quantities when appropriate as well as with some corresponding results for some similar molecules. The r0 structural parameters have been obtained from a combination of the previously reported microwave rotational constants and ab initio predicted parameters.     

Vibrational spectra of cyclopentadienylphosphine: infrared and theoretical studies from DFT anharmonic potentials

Both experimental and theoretical infrared investigations of cyclopentadienylphosphine (CpP) are reported. The infrared spectra (3500-500 cm(-1)) in the gas phase have been recorded at 0.5 cm(-1) resolution. Infrared absorptions bands of the two lowest stable conformers were observed and assigned. Average integrated intensities of isolated and overlapping vibrational bands were also determined experimentally. The vibrational frequencies of the CpP system and its P-dideuterated isotopologue have been calculated by means of density functional theory. The Becke exchange functional and Lee-Yang-Parr correlation functional method with a combination of the two basis sets, namely 6-31+G(d,p) and the correlation-consistent triple-zeta cc-pVTZ set of Dunning, were used. Hybrid B3LYP/B3LYP//cc-pVTZ/6-31+G(d,p) anharmonic frequencies of the fundamental, overtone, and combination transitions were calculated in the 3500-200 cm(-1) area with the use of a variational approach, implemented in the P_Anhar_v1.1 code, to assign the experimental data for each conformer.     

Hydrogen bond, dimerization and vibrational modes in 2-chloro-3-hydroxybenzaldehyde and 3-chloro-4-hydroxybenzaldehyde from vibrational and ab initio studies

Ab initio conformers and dimers have been computed at RHF and B3LYP/6-31G* levels for isomers 2-chloro-3-hydroxybenzaldehyde and 3-chloro-4-hydroxybenzaldehyde to explain the observed infrared absorption and Raman vibrational spectral features in the region 3500-50 cm(-1). The position of the chlorine in ortho position with respect to aldehyde group in 2-chloro-3-hydroxybenzaldehyde yields four distinct conformers; whereas the chlorine in meta position in 3-chloro-4-hydroxybenzaldehyde yields effectively only three conformers. Major spectral features as strong absorptions near 3160-80 cm(-1), down-shifting of the aldehydic carbonyl stretching mode and up-shifting of hydroxyl group's in-plane bending mode are explained using ab initio evidence of O-H?O bond-aided dimerization between the most stable conformers of each molecule. Absorption width of about 700 cm(-1) (～8.28 kJ/mol) of O-H stretching modes suggests a strong hydrogen bonding with the ab initio bond lengths, O-H?O in the range of 2.873-2.832 ?. A strong Raman mode near 110-85 cm(-1) in each molecule is interpreted to be coupled vibrations of pseudo-dimeric trans and cis structures.     

FT-IR and FT-Raman spectroscopic investigation, computed vibrational frequency analysis and IR intensity and Raman activity peak resemblance analysis on 2-nitroanisole using HF and DFT (B3LYP and B3PW91) calculations

Fourier-transform Raman and infrared spectra of 2-nitroanisole are recorded (4000-100 cm(-1)) and interpreted by comparison with respective theoretical spectra calculated using HF and DFT method. The geometrical parameters with C(S) symmetry, harmonic vibrational frequencies, infrared and Raman scattering intensities are determined using HF/6-311++G (d, p), B3LYP/6-311+G (d, p), B3LYP/6-311++G (d, p) and B3PW91/6-311++G (d, p) level of theories. A 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 results of the calculations have been used to simulate IR and Raman spectra for the molecule that showed good agreement with the observed spectra. The SQM method, which implies multiple scaling of the DFT force fields has been shown superior to the uniform scaling approach. The vibrational frequencies and the infrared intensities of the C-H modes involved in back-donation and conjugation are also investigated.     

Vibrational assignment of the spectral data and thermodynamic properties of 2-chloro-4-fluorobenzophenone using DFT quantum chemical calculations

The FT-Raman (3500-100 cm⁻¹) and FT-IR (4000-450 cm⁻¹) spectra of 2-chloro-4-fluorobenzophenone were recorded in the solid phase. Density functional theory calculations with B3LYP/6-31G (d, p) basis set was used to determine the ground state molecular geometries (bond lengths and bond angles), harmonic vibrational frequencies, infrared intensities and Raman activities of this compound. Potential energy distributions (PEDs) and normal modes, for the spectral data computed at B3LYP/6-31G (d, p) level, have also been obtained from force-field calculations. The wavenumbers found after scaling of the force field showed very good agreement with the experimentally determined values. A comparison of the theoretical spectra and experimental FT-IR and FT-Raman spectra of the title molecule has been made and full vibrational assignments of the observed spectra have been proposed. On the basis of vibrational analyses, the thermodynamic properties of title compound at different temperatures have been calculated.     

Spectra and structure of small ring compounds. LXVII vibrational spectra, variable temperature FT-IR spectra of krypton solutions, conformational stability and ab initio calculations of 1-bromosilacyclobutane

The infrared (3,200-30 cm(-1) spectra of gaseous and solid 1-bromosilacyclobutane, c-C3H6SiBrH, have been recorded. Additionally, the Raman spectra of the liquid (3,200- 30 cm(-1) with quantitative depolarization values and the solid have been recorded. Both the equatorial and the axial conformers have been identified in the fluid phases, Variable temperature ( - 105 to - 150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been carried out. From these data the enthalpy difference has been determined to be 182 +/- 18 cm(-1) (2.18 +/- 0.22 kJ/mol) with the equatorial conformer the more stable rotamer and only conformer remaining in the annealing solid. At ambient temperature there is approximately 22% of the axial conformer present in the vapor phase. A complete vibrational assignment is proposed for both conformers based on infrared contours, relative intensities, depolarization values and group frequencies. The vibrational assignments are supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. From the frequencies of the Si-H stretch, the Si-H bond distance of 1.483 A has been determined for both the equatorial and the axial conformers. Complete equilibrium geometries have been determined for both rotamers by ab initio calculations employing the 6-31G(d) and 6-311 +/- G(d,p) basis sets at levels of Hartree Fock (RHF) and/or Moller- Plesset with full electron correlation by the perturbation method to the second order (MP2). The results are discussed and compared to those obtained for some similar molecules.     

Theoretical studies on vibrational spectra of mixed cyanide-halide complexes of platinum(IV) and palladium(IV)

The vibrational spectra of mixed cyanide-halide complexes, M(CN)4X 2 2- and M(CN)5X2- (M=Pt and Pd; X=F, Cl, Br and I), have been systematically investigated by ab initio RHF, B3LYP and MP2 methods with LanL2DZ and SDD basis sets. The calculated vibrational frequencies of platinum complexes are evaluated via comparison with the experimental values. In the infrared frequency region, the C--N stretching vibrational frequencies calculated at B3LYP level with two basis sets are in good agreement with the observed values with deviations, -16-4 cm(-1) for Pt(CN)4X 2 2- and -18 to -2 cm(-1) for Pt(CN)5X2-. However, in far-infrared region, the results obtained at RHF level are better than those calculated at B3LYP and MP2 levels. For RHF/SDD method, the deviations for Ptz.sbnd;X and Ptz.sbnd;C stretching vibrational frequencies are -14-1 and -12 to -2 cm(-1) in the complex Pt(CN)4X2 2-, -19 to -11 and -15-14 cm(-1) in the Pt(CN)5X2- complex, respectively. The vibrational frequencies of palladium(IV) and some platinum(IV) complexes that have not been experimentally reported are predicted.     

Conformational stability, optimized geometries, vibrational and electronic spectra of methacryloyl bromide in ground and excited electronic states

In order to understand conformational isomerism in methacryloyl bromide (MABR) in the ground (S(0)) and the first excited (S(1)) electronic states and to interpret the vibrational and electronic spectra of its conformers in the S(0) state, quantum mechanical calculations using Density Functional Theory (DFT) and RHF methods with extended basis sets 6-31G, 6-31G** and 6-311+G(d,p) have been conducted. In RHF calculations, electron correlation effects have been included at the M?ller-Plesset MP2 level. It is inferred that in both the electronic states the molecule may exist in two isomeric forms-s-trans and s-cis; the former being more stable than the later by about 1.629 kcal mol(-1) in the S(0) state and by about 2.218 kcal mol(-1) in the S(1) state. Electronic transition tends to increase the s-trans/s-cis and s-cis/s-trans, rotational barriers from 7.059 kcal mol(-1) (2468.1 cm(-1)) and 5.428 kcal mol(-1) (1897.8 cm(-1)) in S(0) state to 23.594 kcal mol(-1) (8249.4 cm(-1)) and 21.376 kcal mol(-1) (7473.9 cm(-1)) in the S(1) state. Completely optimized geometries of the two conformers in S(0) state reveal that while there is no significant difference in their bond lengths, some of the bond angles associated with COBr group are appreciably different. Electronic excitation tends to change both the bond lengths and bond angles. Based on suitably scaled DFT and RHF results obtained from the use of 6-31G** and 6-311+G(d,p) basis sets, a complete assignment is provided to the fundamental vibrational bands of both the s-trans and s-cis conformers in terms of frequency, form and intensity of vibrations and potential distribution across the symmetry coordinates in the S(0) state and a comparison has been made with experimental assignments. A theoretical prediction of the electronic transitions in the near UV-region in the two conformers and their tentative assignment has been provided on the basis of CI level calculations using 6-31G basis set.     

Ultrafast infrared spectroscopy of riboflavin: dynamics, electronic structure, and vibrational mode analysis

Femtosecond time-resolved infrared spectroscopy was used to study the vibrational response of riboflavin in DMSO to photoexcitation at 387 nm. Vibrational cooling in the excited electronic state is observed and characterized by a time constant of 4.0 +/- 0.1 ps. Its characteristic pattern of negative and positive IR difference signals allows the identification and determination of excited-state vibrational frequencies of riboflavin in the spectral region between 1100 and 1740 cm (-1). Density functional theory (B3LYP), Hartree-Fock (HF) and configuration interaction singles (CIS) methods were employed to calculate the vibrational spectra of the electronic ground state and the first singlet excited pipi* state as well as respective electronic energies, structural parameters, electronic dipole moments and intrinsic force constants. The harmonic frequencies of the S 1 excited state calculated by the CIS method are in satisfactory agreement with the observed band positions. There is a clear correspondence between computed ground- and excited-state vibrations. Major changes upon photoexcitation include the loss of the double bond between the C4a and N5 atoms, reflected in a downshift of related vibrations in the spectral region from 1450 to 1720 cm (-1). Furthermore, the vibrational analysis reveals intra- and intermolecular hydrogen bonding of the riboflavin chromophore.