Characterization of the nitric acid–water complex in the infrared and near-infrared region at ambient temperatures in carbon tetrachloride

Maroń, Marta K.; Shultz, Mary Jane; Vaida, Veronica

doi:10.1016/j.cplett.2009.03.071

Cited by 5 publications

(3 citation statements)

References 49 publications

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“…An interesting trend observed from the infrared studies involves the intensity of the fundamental and overtone transitions associated with the hydrogen-bonded proton donor stretching coordinate. For example, measurements in liquid phase samples containing OH groups has shown that hydrogen bonding can increase the IR oscillator strength of the OH-stretching fundamentals while leading to a substantial decrease in the intensity of its first overtone compared to that typically found for OH groups of non-hydrogen-bonded (non-H-bonded) molecules. − A similar trend in IR band intensities of H-bonded systems has also been noted in matrix isolation and helium droplet experiments. − Gas-phase measurements of H-bonded systems apparently also support this trend, although the results are less conclusive . Several gas-phase studies have reported that overtone transitions of H-bonded hydroxyl groups become very difficult to detect with increasing H-bond strength and that the intensity enhancement due to H-bonding is limited to the OH-stretching fundamental. − Interestingly, however, even though the number of gas-phase studies on H-bonded systems is quite extensive, published experimental values of absolute integrated absorption cross sections for both the fundamental and overtone transitions involving gas phase H-bonded molecules are rather limited.…”

Section: Introductionmentioning

confidence: 75%

Influence of Intramolecular Hydrogen Bonding on OH-Stretching Overtone Intensities and Band Positions in Peroxyacetic Acid

Hazra

Kuang²,

Sinha

2011

J. Phys. Chem. A

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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.

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Section: Introductionmentioning

confidence: 75%

Influence of Intramolecular Hydrogen Bonding on OH-Stretching Overtone Intensities and Band Positions in Peroxyacetic Acid

Hazra

Kuang²,

Sinha

2011

J. Phys. Chem. A

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“…Recent spectroscopic and quantum chemical studies reveal that the presence of hydrogen bonding increases the oscillator strength of the OH stretching fundamentals and leads to a substantial decrease in the intensity of its first overtone compared to that typically found for OH groups of non-hydrogen-bonded molecules. − Futami et al reported a similar result for the NH stretching vibration mode of pyrrole–pyridine complex . For CH stretching vibrations, however, a hydrogen bonding has only subtle effects on the wavenumber shifts and absorption intensities of both the fundamental and the first overtone of the CH stretching band .…”

Section: Introductionmentioning

confidence: 87%

Combined IR/NIR and Density Functional Theory Calculations Analysis of the Solvent Effects on Frequencies and Intensities of the Fundamental and Overtones of the C═O Stretching Vibrations of Acetone and 2-Hexanone

et al. 2014

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Vibrational overtone studies primarily focus on X-H stretching overtone transitions, where X is an atom like C, O, N, or S. In contrast, the studies on the C ═ O stretching overtones are very scattered. To advance the research in this field, we measured the fundamental, first, and second overtones of the C ═ O stretching vibration of acetone and 2-hexanone in n-hexane, CCl4, and CHCl3, as well as in the vapor phase using FT-IR/FT-NIR spectroscopy. Density functional theory (DFT) calculations have also been performed to help the assignment of the C ═ O stretching bands and to guide interpretation of the experimental results. It was found that the wavenumbers, absorption intensities, and oscillator strengths of the C ═ O stretching bands show marked solvent dependence. In the fundamental and the first overtone regions, the intensities of the C ═ O stretching vibration were found to be pronouncedly more intense than those of the C-H stretching vibration. In the second overtone region, the intensities of the C-H stretching vibration are comparable to those of the C ═ O stretching vibration. The theoretical and observed decrease in integrated intensity upon going from the fundamental to the first overtone of the C ═ O stretching vibration is around 50, which is significantly larger than those of the O-H, C-H, and S-H stretching vibration. Both the calculated and experimental results suggest that excessive weakness in the C ═ O stretching overtone was shown to be a result of both a low anharmonicity and a substantial reduction in the oscillator strength. These results provide new insight into our understanding of the C ═ O stretching vibration.

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“…There is strong interest in intermolecular hydrogen bonding in complexes. − However, room-temperature studies of these weakly bound complexes are complicated by their low equilibrium constants and correspondingly short lifetimes. ,− To counteract this disadvantage, we have in the past investigated intramolecular hydrogen-bond-like interactions by probing OH-stretching overtones. ,,,,,− In the present study, we use room-temperature, vapor-phase OH- and SH-stretching vibrational spectroscopy supported by DFT and ab initio calculations of local mode XH-stretching transitions, abundance of conformers, and bond critical points to investigate the intramolecular interactions in 2ME and EDT.…”

Section: Introductionmentioning

confidence: 99%

Overtone Spectra of 2-Mercaptoethanol and 1,2-Ethanedithiol

Miller

Yekutiel²,

Södergren³

et al. 2010

J. Phys. Chem. A

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Vibrational spectra of vapor-phase 1,2-ethanedithiol and 2-mercaptoethanol were recorded to investigate weak intramolecular interactions. The spectra were recorded with conventional absorption spectroscopy and laser photoacoustic spectroscopy in the 2000-11,000 cm(-1) region. The room temperature spectra of each molecule are complicated by contributions from several conformers. Anharmonic oscillator local-mode calculations of the OH- and SH-stretching transitions have been performed to facilitate assignment of the different conformers in the spectra. We observe evidence of hydrogen-bond-like interactions from OH to S, but not from SH to O or S. The OH to S intramolecular interaction in 2-mercaptoethanol is weak and comparable to that found in the OH to O interaction in ethylene glycol.

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Characterization of the nitric acid–water complex in the infrared and near-infrared region at ambient temperatures in carbon tetrachloride

Cited by 5 publications

References 49 publications

Influence of Intramolecular Hydrogen Bonding on OH-Stretching Overtone Intensities and Band Positions in Peroxyacetic Acid

Influence of Intramolecular Hydrogen Bonding on OH-Stretching Overtone Intensities and Band Positions in Peroxyacetic Acid

Combined IR/NIR and Density Functional Theory Calculations Analysis of the Solvent Effects on Frequencies and Intensities of the Fundamental and Overtones of the C═O Stretching Vibrations of Acetone and 2-Hexanone

Overtone Spectra of 2-Mercaptoethanol and 1,2-Ethanedithiol

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