Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 12, Issue 9, Pages 2259-2265Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.1c00168
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Funding
- National Natural Science Foundation of China [92061203, 21688102]
- Strategic Priority Research Program of Chinese Academy of Sciences (CAS) [XDB17000000]
- International Partnership Program of CAS [121421KYSB20170012]
- CAS [GJJSTD20190002]
- Ministry of Science and Technology of Taiwan [MOST 107-2628-M-001-002-MY4, MOST 108-2639-M-009-001-ASP, MOST 109-2113-M-001-040]
- Academia Sinica
- Academia Sinica Postdoctoral Research Fellowship
- Research Grants Council of Hong Kong SAR Government through a GRF Grant [2130479]
- Dalian Institute of Chemical Physics (DICP) [DCLS201701, DCLS201702]
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The study uses a tunable vacuum ultraviolet free electron laser to unmask the vibrational signatures of dynamic couplings in neutral trimethylamine-water and trimethylamine-methanol complexes. The experimental results show distinct vibrational characteristics in the two complexes, providing direct evidence for dynamic couplings of hydrogen bonds.
Elucidating the dynamic couplings of hydrogen bonds remains an important and challenging goal for spectroscopic studies of bulk systems, because their vibrational signatures are masked by the collective effects of the fluctuation of many hydrogen bonds. Here we utilize size-selected infrared spectroscopy based on a tunable vacuum ultraviolet free electron laser to unmask the vibrational signatures for the dynamic couplings in neutral trimethylamine-water and trimethylamine-methanol complexes, as microscopic models with only one single hydrogen bond holding two molecules. Surprisingly broad progression of OH stretching peaks with distinct intensity modulation over similar to 700 cm(-1) is observed for trimethylamine-water, while the dramatic reduction of this progression in the trimethylamine-methanol spectrum offers direct experimental evidence for the dynamic couplings. State-of-the-art quantum mechanical calculations reveal that such dynamic couplings are originated from strong Fermi resonance between the stretches of hydrogen-bonded OH and several motions of the solvent water/ methanol, such as translation, rocking, and bending, which are significant in various solvated complexes commonly found in atmospheric and biological systems.
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