Effect of Temperature on the OH-Stretching Bands of the Methanol Dimer
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
We present a conceptually simple model for understanding the significant spectral changes that occur with the temperature in the infrared spectra of hydrogen-bound complexes. We have measured room-temperature spectra of the methanol dimer and two deuterated isotopologues in the OH(D)-stretching region. We correctly predict spectral changes observed in the gas phase for the bound OH stretch in the methanol dimer from jet-cooled to room temperature and corroborate this with experimental and theoretical results for deuterated isotopologues. The origin of the observed spectral features is explained based on a reduced-dimensional vibrational model, which includes the two high-frequency OH stretches, the two methyl torsions, and the six intermolecular low-frequency vibrations. Key to the success of the model is a new coordinate definition to describe the intrinsic large-amplitude curvilinear motion of low-frequency vibrations. Despite the deceivingly simple appearance of the room temperature bound OH-stretching fundamental band, it consists of ∼107 vibrational transitions.
Originalsprog | Engelsk |
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Tidsskrift | Journal of Physical Chemistry A |
Vol/bind | 128 |
Udgave nummer | 2 |
Sider (fra-til) | 392-400 |
Antal sider | 9 |
ISSN | 1089-5639 |
DOI | |
Status | Udgivet - 2023 |
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© 2024 American Chemical Society.
ID: 381233493