AI Article Synopsis
- Tertiary amines are effective hydrogen bond acceptors, significantly affecting the vibrational properties of water when they interact.
- When water donates an OH group, its vibrational frequency decreases, leading to complex phenomena such as Fermi resonance and combination transitions, which broaden the spectral features of hydrogen-bonded amine complexes.
- Using Fourier transform infrared spectroscopy, researchers have identified unique signatures in specific amine monohydrates that indicate rapid energy flow within the hydrogen-bonded system.
Article Abstract
Tertiary amines are strong hydrogen bond acceptors. When a water molecule donates one of the OH groups, its in-phase stretching vibration wavenumber is decreased to such an extent that it comes close to the water bending overtone. This gives rise to anharmonic phenomena such as classical Fermi resonance, resonance with multiple-quantum dark states, or combination transitions with low-frequency intermolecular modes. These effects, which contribute to the spectral breadth of room-temperature hydrogen-bonded amine complexes, are disentangled by Fourier transform infrared spectroscopy in pulsed supersonic slit jet expansions. Monohydrates of the amines quinuclidine, -methylpyrrolidine, -methylpiperidine, and dimethylcyclohexylamine exhibit systematic mode coupling signatures. These suggest relatively fast energy flow out of the excited OH stretching fundamental into intra- and intermolecular degrees of freedom of the hydrogen-bonded water molecule. Trimeric complexes are spectroscopically separated from the amine monohydrates.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10658632 | PMC |
| http://dx.doi.org/10.1021/acs.jpclett.3c02517 | DOI Listing |
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