Hydroxyl bands in the infra-red spectra of organophosphoric and phosphinic acids

Detoni, S.; Hadži, D.

doi:10.1016/0371-1951(64)80095-3

Cited by 59 publications

(12 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The three broad absorptions at 2640, 2232 (center of a doublet), and 1685 cm À1 in the liquid have been assigned as the dimer O-H stretch mixing with the first overtones of the inplane (;1200 cm À1 ) and out-of-plane (;900 cm À1 ) O-H bends. [32][33][34] The corresponding features in the Factor 1 spectrum appear at 2665 and 2390 cm À1 with no distinct feature near 1700 cm À1 . The intensity of this region is greater relative to the C-H stretch absorptions than it is in the liquid.…”

Section: Solvent Leaching Testmentioning

confidence: 99%

Multivariate Curve Resolution Applied to Infrared Reflection Measurements of Soil Contaminated with an Organophosphorus Analyte

Gallagher

Blake²,

Gassman³

et al. 2006

Appl Spectrosc

View full text Add to dashboard Cite

Multivariate curve resolution (MCR) is a powerful technique for extracting chemical information from measured spectra of complex mixtures. A modified MCR technique that utilized both measured and second-derivative spectra to account for observed sample-to-sample variability attributable to changes in soil reflectivity was used to estimate the spectrum of dibutyl phosphate (DBP) adsorbed on two different soil types. This algorithm was applied directly to measurements of reflection spectra of soils coated with analyte without resorting to soil preparations such as grinding or dilution in potassium bromide. The results provided interpretable spectra that can be used to guide strategies for detection and classification of organic analytes adsorbed on soil. Comparisons to the neat DBP liquid spectrum showed that the recovered analyte spectra from both soils showed spectral features from methyl, methylene, hydroxyl, and P=O functional groups, but most conspicuous was the absence of the strong PO-(CH2)3CH3 stretch absorption at 1033 cm(-1). These results are consistent with those obtained previously using extended multiplicative scatter correction.

show abstract

Section: Solvent Leaching Testmentioning

confidence: 99%

Multivariate Curve Resolution Applied to Infrared Reflection Measurements of Soil Contaminated with an Organophosphorus Analyte

Gallagher

Blake²,

Gassman³

et al. 2006

Appl Spectrosc

View full text Add to dashboard Cite

show abstract

“…The corresponding values from X-ray diffraction are also given in the table for comparison. The molecular structure of the 0.975 0.978 C 5 -C 6 -C 7 121.0 120.5 C 6 -C 7 -C 8 -C 9 0.11 0.25 C 2 -C 5 1.519 1.519 C 6 -C 7 -C 8 119.9 119.9 C 7 -C 8 -C 9 -C 10 0.19 0.27 C 5 -C 6 1.401 1.393 C 7 -C 8 -C 9 119.5 119.9 C 8 -C 9 -C 10 -C 5 0.06 0.41 C 6 -C 7 1.395 1.383 C 8 -C 9 -C 10 120.4 120.1 C 9 -C 10 -C 5 -C 6 0.17 0.54 C 7 -C 8 1.394 1.379 C 9 -C 10 -C 5 120.4 120.1 C 2 -C 5 -C 6 -H 6 3.1 6.5 C 8 -C 9 1.395 1.395 C 5 -C 6 -H 6 119.4 119.5 C 5 -C 6 -C 7 -H 7 179.8 172.9 C 9 -C 10 1.394 1.382 C 6 -C 7 -H 7 119.7 117.8 C 6 -C 7 -C 8 -H 9 179.8 176.0 C 10 -C 5 1.402 1.397 C 7 -C 8 -H 9 120.2 121.9 C 7 -C 8 -C 9 -H 9 179.5 177.4 C 6 -H 6 1.088 0.933 C 8 -C 9 -H 10 120.0 126.9 C 8 -C 9 -C 10 -H 10 178.8 177.3 C 7 -H 7 1.086 1.027 C 9 -C 10 -H 11 119.8 115.6 C 8 -H 9 1.086 1.077 C 9 -H 9 1.086 0.956 C 10 -H 10 1.086 0.996 compound with the atom numbering scheme adopted in the computations is shown in Fig. 3.…”

Section: Crystallographic and Molecular Structuresmentioning

confidence: 99%

Dimerisation and vibrational spectroscopic properties of (RS)-phenylsuccinic acid

Sajan¹,

Fischer

Joe³

et al. 2006

J. Raman Spectrosc.

View full text Add to dashboard Cite

Single crystals of (RS)-phenylsuccinic acid (RSPSA) were grown by the slow evaporation technique and vibrational spectral analysis was carried out using near-IR Fourier transform Raman and Fourier transform IR spectroscopy. The density functional theoretical (DFT) computations were also performed at the B3LYP/6-31G(d) level to derive the equilibrium geometry, vibrational wavenumbers, intensities and atomic charges. Vibrational spectral investigation confirmed the formation of cyclic dimers in the crystal, with the carboxyl groups of each acid molecule being hydrogen bonded to those of the adjacent molecules. Each molecule is connected to two other molecules, forming infinite chains. The wavenumber difference observed between the carbonyl modes in the IR and Raman spectra might be attributed to the intramolecular association based on C O· · ·H type hydrogen bonding in the molecule. In a hydrogenbonded carbonyl, resonance can occur, which places a partial negative charge on the oxygen atom accepting the hydrogen bond and a positive charge on the atom donating the hydrogen. The resulting partial 'transfer of allegiance' of the proton enhances resonance and lowers the carbonyl stretching wavenumber. The O-H stretching vibrational wavenumber is red-shifted owing to the formation of strong O-H· · ·O hydrogen bonds by hyperconjugation between carbonyl oxygen lone electron pairs and O-H s * antibonding orbitals. Vibrational analysis was used to investigate the C-H· · ·O interaction and electronic effects, induction of the methylene group by an adjacent electronegative atom and the resulting increase of stretching mode wavenumbers and decrease of infrared intensities.

show abstract

“…1,3,4 For weak and medium strength hydrogen bonds, both the frequency shift and width of the OH stretching vibration can be several hundred wavenumbers, but strong hydrogen bonds can lead to much broader spectral features with remarkable multi-hump structures. [5][6][7] Hydrogen-bonded dimers in nonpolar solvents form ideal model systems for studying the effect of the hydrogen-bonding strength on vibrational modes. Such dimers exhibit a number of unusual vibrational features.…”

Section: Introductionmentioning

confidence: 99%

Origin of the 900 cm−1 broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids

Hoozen

Petersen

2015

The Journal of Chemical Physics

View full text Add to dashboard Cite

Medium and strong hydrogen bonds are common in biological systems. Here, they provide structural support and can act as proton transfer relays to drive electron and/or energy transfer. Infrared spectroscopy is a sensitive probe of molecular structure and hydrogen bond strength but strongly hydrogen-bonded structures often exhibit very broad and complex vibrational bands. As an example, strong hydrogen bonds between carboxylic acids and nitrogen-containing aromatic bases commonly display a 900 cm(-1) broad feature with a remarkable double-hump structure. Although previous studies have assigned this feature to the OH, the exact origin of the shape and width of this unusual feature is not well understood. In this study, we present ab initio calculations of the contributions of the OH stretch and bend vibrational modes to the vibrational spectrum of strongly hydrogen-bonded heterodimers of carboxylic acids and nitrogen-containing aromatic bases, taking the 7-azaindole--acetic acid and pyridine--acetic acid dimers as examples. Our calculations take into account coupling between the OH stretch and bend modes as well as how both of these modes are affected by lower frequency dimer stretch modes, which modulate the distance between the monomers. Our calculations reproduce the broadness and the double-hump structure of the OH vibrational feature. Where the spectral broadness is primarily caused by the dimer stretch modes strongly modulating the frequency of the OH stretch mode, the double-hump structure results from a Fermi resonance between the out of the plane OH bend and the OH stretch modes.

show abstract

Hydroxyl bands in the infra-red spectra of organophosphoric and phosphinic acids

Cited by 59 publications

References 16 publications

Multivariate Curve Resolution Applied to Infrared Reflection Measurements of Soil Contaminated with an Organophosphorus Analyte

Multivariate Curve Resolution Applied to Infrared Reflection Measurements of Soil Contaminated with an Organophosphorus Analyte

Dimerisation and vibrational spectroscopic properties of (RS)-phenylsuccinic acid

Origin of the 900 cm−1 broad double-hump OH vibrational feature of strongly hydrogen-bonded carboxylic acids

Contact Info

Product

Resources

About