The meaning of the very different OH bandshapes in infrared fundamental and overtone regions of H-bonded methanol

Infrared spectra of methanol in solvents were discussed in the fundamental and overtone region in dependence on the temperature. One absorption band is observed in the fundamental region of the OH stretching vibration, however, the overtone band is splitted into two or more bands. The intensity ratio of the overtone bands changes characteristically with the temperature and with the H-bond strength. This behavior will be explained by different OH transitions, taking into account the OO vibration. A modified Lippincott-Schroeder procedure was used for the calculations of energy values. The splitting of the overtone bands could be assigned to the transitions E(v=0,v′) → E(v=2,v′) and E(v=0,v′) » E(v=2,v′+1), with v′ as OO vibrational quantum-number.     

Spectral evidence of solid state interactions in mixed dimethyl sulfone-water ices

Infrared spectra of solid mixtures of dimethyl sulfone and ice were studied. A comparison of the spectra to those of the pure solids indicates bands attributable to two solid-solid interactions-a stronger and a weaker one—both centered on the OH?OS moieties. The bonded ν(OH) stretch assigned to the stronger interaction is part of the broad ‘3μ’ ice band and its wavenumber value is close to that reported previously for the 1:1 ((CH₃)₂SO₂)·H₂O) complex isolated in rare gas matrices. The weaker interaction is discerned at higher wavenumbers as a very low intensity feature, only slightly shifted from the free ν(OH) band positions.     

Raman and FT IR ATR study of diethylsulfoxide/water mixtures

The Raman and FT IR ATR spectra of diethylsulfoxide (DESO)-water mixtures in the SO and C-H stretching vibration regions at different molar ratios are considered. Noticeable changes are observed in the ν_SO region, suggesting the existence of strong H-bonds between DESO and water molecules; on the contrary the ν_CH bands change only in a less extent, supporting the existence of SO?HC hydrogen bonds in pure DESO that gradually break in the presence of water. In addition, FT IR measurements confirm the existence of ‘free’ SO group at low concentrations of DESO.The results obtained are well explainable in frame of the cluster-structure model of liquid water.     

Influence of intramolecular hydrogen bonding on OH-stretching overtone intensities and band positions in peroxyacetic acid

Vapor phase absorption spectra and integrated band intensities of the OH stretching fundamental as well as first and second overtones (2ν(OH) and 3ν(OH)) in peroxyacetic acid (PAA) have been measured using a combination of FT-IR and photoacoustic spectroscopy. In addition, ab initio calculations have been carried out to examine the low energy stable conformers of the molecule. Spectral assignment of the primary features appearing in the region of the 2ν(OH) and 3ν(OH) overtone bands are made with the aid of isotopic substitution and anharmonic vibrational frequency calculations carried out at the MP2/aug-cc-pVDZ level. Apart from features associated with the zeroth-order OH stretch, the overtone spectra are dominated by features assigned to combination bands composed of the respective OH stretching overtone and vibrations involving the collective motion of several atoms in the molecule resulting from excitation of the internal hydrogen bonding coordinate. Integrated absorption cross section measurements reveal that internal hydrogen bonding, the strength of which is estimated to be ～20 kJ/mol in PAA, does not result in a enhanced oscillator strength for the OH stretching fundamental of the molecule, as is often expected for hydrogen bonded systems, but does cause a precipitous drop in the oscillator strength of its 2ν(OH) and 3ν(OH) overtone bands, reducing them, respectively, by a factor of 165 and 7020 relative to the OH stretching fundamental.     

Vibrational spectra of transition metal hexafluoride crystals. II. Two-particle and mixed crystal spectra as techniques for determination of densities

In part II of this series two techniques for obtaining densities of exciton states are discussed: heavily doped crystals and two-particle overtone and combination bands. It is demonstrated through Raman spectra and calculations that (ν_i + ν₁) combination bands yield very nearly true density of states functions for ν_i in the case for which ν₁ is essentially dispersionless. The mixed crystal method for density of states determinations is compared to the combination band technique and approximate mixed crystal concentrations appropriate for such studies can be calibrated for individual bands. It is pointed out that the overtone method, whenever applicable, is both simpler and more accurate for exciton state studies. Detailed analyses of ν₁ and 2ν₁ show that the major contribution to overtone intensity comes from the second order polarizability derivative and not anharmonic contributions.     

Spectroscopic detection of free “lone-pair” groups or terminal methanol molecules in methanol solutions

When basic aprotic solvents are added to methanol they become hydrogen bonded, and there is a consequent growth in non-bonded lone-pairs, (LP)_free. Although corresponding non-bonded OH groups, (OH)_free, have been detected for alcohols and for water, using overtone infrared spectroscopy, no different spectroscopic evidence for (LP)_free groups has previously been reported. We have found that unique OH stretching bands develop when strongly basic solvents such as dimethylsulphoxide are added to methanol. Band maxima assigned to (LP)_free groups occur at 3440 cm^?1 in the fundamental and 6790 cm^?1 in the overtone region. These are at considerably higher frequencies than those for bulk methanol (3340 cm^?1 and 6600 cm^?1) showing that the hydrogen bond is weakened in this unit, as expected. Proton resonance shifts for the OH protons of methanol on adding basic aprotic cosolvents are reported, and explained in terms of these results.     

Identification of an OH,CH combination band in the near infrared spectrum of ethanol

The identification of an OH_stretch/CH_stretch combination band in the near infrared (n.i.r.) spectrum of ethanol is based on comparison of the calculated positions of overtone and combination bands with the n.i.r. spectra of C₂H₅OH, C₂H₅OD, CH₃OH and CH₃OD.     

Kink motion in poly(vinylidene fluoride) form I

The diffuse-streak x-ray scattering intensity from poly(vinylidene fluoride) form I, which is caused by kink bands with GT_n? (n odd) conformation contained in the crystallite, decreases with increasing temperature, while the intensity of the 001 reflection does not change. This is attributed to the disappearance of the kink bands in the crystallite, not to partial melting of crystallites containing kink bands. The disappearance of the kink bands suggests that kink motion takes place in the crystallite. Plots of the intensity of diffuse-streak scattering, estimated from the asymmetric part of the 001 reflection, against 1/T roughly give ΔH_v = ?4.6 kcal/mol. This suggests that the kink band is energetically more stable than the regular structure of form I.     

Mass effects on the applicability of a local mode description - an analysis of the high energy overtone spectra of difluoro-, dichloro-, dibromo-, and diiodomethane

The overtone spectra of difluoro-, dichloro-, dibromo-, and diiodomethane are measured in the liquid phase from 6000 to 12000 A. The principal absorption bands in the three latter molecules are assigned to Δυ_CH = 3, 4, 5 and 6 in a pure local mode CH-stretching oscillator. Combination bands between these CH overtones are identified with either local mode combinations or local mode—normal mode combinations. The harmonic local mode frequency and the diagonal local mode anharmonicity constant are obtained for all four molecules. The change in harmonic frequency with halogen substitution is discussed. Off-diagonal local mode and off-diagonal local mode—normal mode anharmonicity constants are derived and their relative magnitudes discussed. The effects of changing mass on the spectrum are pointed out. In particular, it is demonstrated that the Δυ_CH = 3 transition in difluoromethane corresponds to what is expected on the basis of symmetry allowed normal mode components rather than what is expected from the multiple excitation of a local oscillator.     

Interaction energy and the shift in OH stretch frequency on hydrogen bonding for the H2O → H2O,CH3OH → H2O,and H2O → CH3OH dimers

The ability to use calculated OH frequencies to assign experimentally observed peaks in hydrogen bonded systems hinges on the accuracy of the calculation. Here we test the ability of several commonly employed model chemistries—HF, MP2, and several density functionals paired with the 6‐31+G(d) and 6‐311++G(d,p) basis sets—to calculate the interaction energy (D_e) and shift in OH stretch fundamental frequency on dimerization (δ(ν)) for the H₂O → H₂O, CH₃OH → H₂O, and H₂O → CH₃OH dimers (where for X → Y, X is the hydrogen bond donor and Y the acceptor). We quantify the error in D_e and δ(ν) by comparison to experiment and high level calculation and, using a simple model, evaluate how error in D_e propagates to δ(ν). We find that B3LYP and MPWB1K perform best of the density functional methods studied, that their accuracy in calculating δ(ν) is ≈ 30–50 cm^?1 and that correcting for error in D_e does little to heighten agreement between the calculated and experimental δ(ν). Accuracy of calculated δ(ν) is also shown to vary as a function of hydrogen bond donor: while the PBE and TPSS functionals perform best in the calculation of δ(ν) for the CH₃OH → H₂O dimer their performance is relatively poor in describing H₂O → H₂O and H₂O → CH₃OH. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Vibrational spectra of 2-methylpropanal: Assignments,self-associations and solvent effects

Raman and infrared spectra of 2-methylpropanal (CH₃)₂CHCHO, (CH₃)₂CDCHO and (CH₃)₂CHCDO in different physical states (liquid, solid and solution) have been investigated between 4000 and 40 cm⁻¹. A complete assignment is carried out on the basis of one predominant conformer (anticlinal) in equilibrium with another less stable one (synperiplanar). Some vibrational modes of the synperiplanar form are identified. The CO stretching region is carefully examined. The complex structure of this band as a function of the physical state of the pure aldehyde and the polarity of the solvent for solutions is discussed. The structure can be explained by Fermi resonances between combinations and the fundamental νCO mode. In the pure liquid, as well as in solution, the broadness of the band can be due to random dipolar interactions. In polar basic solvents (CH₃CN and DMSO), these interactions implicate both aldehyde and solvent. When the solvent is slightly acidic (HCCl₃), weak hydrogen bonds between the aldehydic group and the solvent may occur. Moving from the liquid to the solid state, in addition to the fact that the less stable conformer disappears, molecular association between the CO groups by charge transfer may account for the observed changes.     

High resolution infrared study of D2CO in the region of 1780–2400 cm−1: assignment and preliminary analysis

A high resolution spectrum of the formaldehyde D₂¹²CO molecule in the range from 1780 to 2400 cm⁻¹ has been recorded by a Fourier transform infrared spectrometer. The measured region covers the stretching fundamental bands ν₁ and ν₅ and the first overtone and combination bands 2ν₄, ν₄+ν₆, 2ν₆, ν₃+ν₄, ν₃+ν₆, and 2ν₃ which correspond to double excitations of deformational quanta. About 9600 transitions were assigned to the eight mentioned vibrational bands. Preliminary analysis with J′<10 of the obtained assignments was made, and the values of the band centers and the main rotational, centrifugal distortion, and resonance interaction parameters were estimated.     

Benefits of near-infrared spectroscopy for characterization of selected organo-montmorillonites

The potential of near infrared (NIR) spectroscopy in characterization of organically modified clay minerals is introduced. Selected organo-clays, possibly perspective fillers in clay polymer nanocomposites, were prepared from Na-montmorillonite and different surfactants containing octylammonium chain(s), hexadecylammonium chain(s) or a benzene ring with or without a reactive double bond. Based on the stretching (ν) and bending (δ) vibrations observed in the middle IR (MIR) region, the first overtone (2νXH) and combination (ν + δ)XH modes of XH groups (X = O, C, N) are identified. The effect of larger alkylammonium cations on the vibrations of Si-O and OH bonds in montmorillonite layers is observed. The changes in the intensity of the (ν + δ)H₂O band near 5250 cm⁻¹ allows for comparison of the amount of water adsorbed on the montmorillonite surface. The water content decreases with the size of the organic cation reflecting increasing hydrophobicity of the montmorillonite surface. The NIR region shows the 2νCH₃ and 2νCH₂ bands in the 5900-5500 cm⁻¹ region, an upward shift is observed for the complex band due to 2νCH(Ar) of aromatic benzene ring. The NIR spectra are extremely useful in identification of NH₂⁺, NH⁺ and vinyl groups, which are difficult to recognize in the MIR spectra of organo-clays due to overlapping with other absorption bands. The intense bands corresponding to overtones and combination vibrations of NH₃⁺ and NH₂⁺ groups are found in the 6600-6050 cm⁻¹ and 5000-4600 cm⁻¹ regions, the (ν + δ)NH⁺ is unambiguously identified near 4750 cm⁻¹. The characteristic band assigned to 2νCH₂ in H₂CC is detected near 6130 cm⁻¹.     

FTIR spectra of the 2ν4, ν4 + ν6 and 2ν6 bands of formaldehyde

High resolution IR spectra of the overtones and the combination band of the ν₄ and ν₆ modes of formaldehyde (2ν₄, ν₄ + ν₆ and 2ν₆) were measured in the region of 2200–2650 cm⁻¹ using FTIR. The combination band ν₄ + ν₆, whose dipole transition is forbidden from molecular symmetry, was observed due to the intensity borrowed from the other bands. The observed frequencies were analysed by a Hamiltonian in which A-type Coriolis interactions and Darling—Dennison interaction were taken into account. The ratio and the relative signs of the transition dipole moments of the overtone bands, μ_2ν4 and μ_2ν6, have been determined by analysing the intensity distribution of the vibration—rotation lines.     

Vibrational overtone spectroscopy, energy levels, and intensities of (CH3)3C-C≡C-H

The vibrational overtone spectra of the acetylenic (Δυ = 4, 5) and methyl (Δυ = 5, 6) C-H stretch transitions of tert-butyl acetylene [(CH(3))(3)C-C≡C-H] were obtained using the phase shift cavity ring down (PS-CRD) technique at 295 K. The C-H stretch fundamental and overtone absorptions of the acetylenic (Δυ = 2 and 3) and methyl (Δυ = 2-4) C-H bonds have been obtained using a Fourier transform infrared and near-infrared spectrophotometer. Harmonic frequency ω(ν(1)) and anharmonicities x(ν(1)) and x(ν(1), ν(24)) are reported for the acetylenic C-H bond. Molecular orbital calculations of geometry and vibrational frequencies were performed. A harmonically coupled anharmonic oscillator (HCAO) model was used to determine the overtone energy levels and assign the absorption bands to vibrational transitions of methyl C-H bonds. Band strength values were obtained experimentally and compared with intensities calculated in terms of the HCAO model where only the C-H modes are considered. No adjustable parameters were used to get order of magnitude agreement with experimental intensities for all pure local mode C-H transitions.     

Analysis of the ν2 :ν3 + ν4 Fermi resonance in CH3CN isotopic species in solution

Infrared bands due to ν₃ + ν₄, ν₂, ν₃ and ν₄ were recorded for the species CH₃CN, ¹³CH₃CN, CH₃¹³CN and CH₃C¹⁵N in the solvents carbon tetrachloride, chloroform, benzene, pyridine and dimethyl sulphoxide. Values of W₂₃₄ were extracted by the modified Winther method, which are slightly less, 11.2–11.9 cm⁻¹, than the value in the gas, 12.15 cm⁻¹. Relative intensity measurements of ν₃ + ν₄ and ν₂ in CCl₄ are compatible with an unperturbed intensity ratio, I_{ν3 + ν4}/ I_ν2 of ∼ 0.03. The fallibility of the infrared intensity method for determining W, and the need for precise frequency data in the Winther method, are stressed.     

Infrared spectroscopic studies of hydrogen-bonded complexes in cryogenic sulutions

We have measured the ν_s(OH) band parameters of the IR absorption spectra for a wide variety of hydrogen-bonded (HB) complexes of CH₃OH(D), CF₃CH₂OH, and (CF₃)₃COH(D) with some simplest representatives of various classes of bases in Xe and Kr in the temperature range 120–270 K. The ν_s(OH) absorption bands of the HB complexes in solution in atomic solvents have been demonstrated to be narrower by a factor of 2 to 4 than in molecular solvents at the same temperature. The fact that the ν_s(OH) bandwidths in Xe and in the gas phase at similar temperatures are practically the same indicates that these bandwidths are in both cases governed mainly by the contribution of “hot transitions” from a sequence of excited levels of the ν_β low-frequency bending mode of the hydrogen bond. The other characteristic features revealed for the complexes under study in liquid Xe and Kr at ν_s(OH) frequency shifts up to 500 cm⁻¹ include: (1) slight temperature dependence of the ν_s(OH) bandwidth (0.1–0.3 cm⁻¹/K), (2) almost “normal” isotope frequency ratio ν_s(OH)/ν_s(OD) (1.34–1.36) and (3) low ν_s(OH) temperature shift values (0.1–0.4 cm⁻¹/K).     

Combined DFT with NBO and QTAIM studies on the hydrogen bonds in (CH<Subscript>3</Subscript>OH)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 2–8) clusters

The (CH₃OH) _n (n = 2–8) clusters formed via hydrogen bond (H-bonds) interactions have been studied systemically by density functional theory (DFT). The relevant geometries, energies, and IR characteristics of the intermolecular OH···O H-bonds have been investigated. The quantum theory of atoms in molecule (QTAIM) and natural bond orbital (NBO) analysis have also been applied to understand the nature of the hydrogen bonding interactions in clusters. The results show that both the strength of H-bonds and the deformation are important factors for the stability of (CH₃OH) _n clusters. The weakest H-bond was found in the dimer. The strengths of H-bonds in clusters increase from n = 2 to 8, moreover, the strengths of H-bonds in (CH₃OH) _n (n = 4–8) clusters are remarkably stronger than those in (CH₃OH) _n (n = 2, 3) clusters. The small differences of the strengths of H-bonds among (CH₃OH) _n (n = 6–8) clusters indicate that a partial covalent character is attributed to the H-bonds in these clusters. The linear relationships between the electron density of BCP (ρ_b) and the H···O bond length of H-bonds as well as the second-perturbation energies E(2) have also been investigated and used to study the nature of H-bonds, respectively.     

Solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration of pyrrole studied by near-infrared/infrared spectroscopy and DFT calculations

Near-infrared (NIR) and IR spectra were measured for pyrrole in CCl(4), CHCl(3), and CH(2)Cl(2) to study solvent dependence of absorption intensities and wavenumbers of the fundamental and first overtone of NH stretching vibration. It was found that the wavenumbers of the NH fundamental and its first overtone decrease in the order of CCl(4), CHCl(3), and CH(2)Cl(2), which is the increasing order for of the dielectric constant of the solvents. Their absorption intensities increase in the same order, and the intensity increase is more significant for the fundamental than the overtone. These results for the solvent dependence of the wavenumbers and absorption intensities of NH stretching bands of pyrrole are quite different from those due to the formation of hydrogen bonds. Quantum chemical calculations of the wavenumbers and absorption intensities of NH stretching bands by using the 1D Schr?dinger equation based on the self-consistent reaction field (SCRF)/isodensity surface polarized continuum model (IPCM) suggest that the decreases in the wavenumbers of both the fundamental and the overtone of the NH stretching mode with the increase in the dielectric constant of the solvents arise from the anharmonicity of vibrational potential and their intensity increases come from the gradual increase in the slope of the dipole moment function.