期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 31, 页码 13116-13121出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202004686
关键词
2D sum-frequency generation; ab-initio molecular dynamics; energy transfer; solid; liquid interfaces
资金
- ERC [336679]
- Deutsche Forschungsgemeinschaft (DFG) [TRR 146]
- High Performance Computing Center (HLRS) Stuttgart [2DSFG]
- European Research Council (ERC) [336679] Funding Source: European Research Council (ERC)
We investigate the dynamics of water in contact with solid calcium fluoride, where at low pH, localized charges can develop upon fluorite dissolution. We use 2D surface-specific vibrational spectroscopy to quantify the heterogeneity of the interfacial water (D2O) molecules and provide information about the sub-picosecond vibrational-energy-relaxation dynamics at the buried solid/liquid interface. We find that strongly H-bonded OD groups, with a vibrational frequency below 2500 cm(-1), display very rapid spectral diffusion and vibrational relaxation; for weakly H-bonded OD groups, above 2500 cm(-1), the dynamics slows down substantially. Atomistic simulations based on electronic-structure theory reveal the molecular origin of energy transport through the local H-bond network. We conclude that strongly oriented H-bonded water molecules in the adsorbed layer, whose orientation is pinned by the localized charge defects, can exchange vibrational energy very rapidly due to the strong collective dipole, compensating for a partially missing solvation shell.
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