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Journal article
Tuning the vibrational coupling of H3O+ by changing its solvation environment
Physical chemistry chemical physics : PCCP, Vol.18(44), pp.30721-30732
01/01/2016
PMID: 27791214
Web of Science ID: WOS:000388492900052
Abstract
This study demonstrates how the intermode coupling in the hydronium ion (H3O+) is modulated by the composition of the first solvation shell. A series of rare gas solvated hydronium ions (H3O+ Rg(3), where Rg = Ne, Ar, Kr, and Xe) is examined via reduced-dimensional anharmonic vibrational (RDAV) ab initio calculations. We considered six key vibrational normal modes, namely: a hindered rotation, two H-O-H bends, and three O-H stretches. Between the O-H stretches and the H-O-H bends, the first is more sensitive to solvation strength. Our calculations revealed that the Fermi resonance between the first overtones of O-H bends and the fundamentals of O-H stretches led to complex spectral features from 3000 to 3500 cm(-1). Such an interaction is not only sensitive to the type of rare gas messengers surrounding the H3O+ ion, it also exhibits an anomalous H -> D isotope effect. Although it is accepted that visible combination tones (similar to 1900 cm(-1)) arise from the complex coupling between the hindered rotation and the H-O-H bends, the origin of their intensities is not yet clearly understood. We found that the intensity of these combination tones could be much stronger than their fundamental H-O-H bends. Within our theoretical framework, we tracked the combination tone's intensity back to the asymmetric O-H stretches. This simple notion of intensity borrowing is confirmed by examining eight complexes (H3O+center dot Rg(3) and D3O+center dot Rg(3)) with spectral features awaiting experimental confirmations.
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Details
- Title
- Tuning the vibrational coupling of H3O+ by changing its solvation environment
- Publication Details
- Physical chemistry chemical physics : PCCP, Vol.18(44), pp.30721-30732
- Resource Type
- Journal article
- Publisher
- Royal Society of Chemistry
- Number of pages
- 12
- Grant note
- Academia SinicaMinistry of Science and Technology (MOST) of Taiwan: MOST101-2113-M-001-023-MY3, MOST104-2113-M-001-017 Taiwan International Graduate Program (TIGP)National Center for High-Performance Computing (NCHC)
This work was financially supported by various grants from Academia Sinica and the Ministry of Science and Technology (MOST) of Taiwan under MOST101-2113-M-001-023-MY3 and MOST104-2113-M-001-017. JAT would like to thank Taiwan International Graduate Program (TIGP) for a scholarship and MOST for travel support (MOST-103-2922-I-007-213). Computational resources are supported in part by the National Center for High-Performance Computing (NCHC). We wish to thank Dr Kaito Takahashi and Dr Kopin Liu for the fruitful discussions related to this project. We would like to express our gratitude to Dr Masato Morita for the DVR solver.
- Identifiers
- WOS:000388492900052; 99381548018906600
- Academic Unit
- Chemistry; Hal Marcus College of Science and Engineering
- Language
- English