J. Phy Chem. Lett, 2016, 7 (22), pp 4591-4595
Jan Schaefer, Ellen H. G. Backus, Yuki Nagata, Mischa Bonn
Vibrational coupling is relevant not only for dissipation of excess energy after chemical reactions but also for elucidating molecular structure and dynamics. It is particularly important for O–H stretch vibrational spectra of water, for which it is known that in bulk both intra- and intermolecular coupling alter the intensity and line shape of the spectra. In contrast with bulk, the unified picture of the inter/intra-molecular coupling of O–H groups at the water–air interface has been lacking. Here, combining sum-frequency generation experiments and simulation for isotopically diluted water and alcohols, we unveil effects of inter- and intramolecular coupling on the vibrational spectra of interfacial water. Our results show that both inter- and intramolecular coupling contribute to the O–H stretch vibrational response of the neat H2O surface, with intramolecular coupling generating a double-peak feature, while the intermolecular coupling induces a significant red shift in the O–H stretch response.