Dissecting the hydrogen bond network of water: Charge transfer and nuclear quantum effects

• 成果类型: Article
• 署名作者: Flor, Mischa; Wilkins, David M.; de la Puente, Miguel; Laage, Damien; Cassone, Giuseppe; Hassanali, Ali; Roke, Sylvie
• 署名单位: Swiss Federal Institutes of Technology Domain; Ecole Polytechnique Federale de Lausanne; Swiss Federal Institutes of Technology Domain; Ecole Polytechnique Federale de Lausanne; Queens University Belfast; Sorbonne Universite; Consiglio Nazionale delle Ricerche (CNR); Istituto per i Processi Chimico-Fisici (IPCF-CNR); Abdus Salam International Centre for Theoretical Physics (ICTP)
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-9943
• DOI: 10.1126/science.ads4369
• 发表日期: 2024-12-06
• 关键词: hyper-raman scattering; liquid water; vibrational signatures; bending mode; DYNAMICS; spectroscopy; frequency; temperature; spectrum; light

摘要

The molecular structure of water is dynamic, with intermolecular hydrogen (H) bond interactions being modified by both electronic charge transfer and nuclear quantum effects (NQEs). Electronic charge transfer and NQEs potentially change under acidic or basic conditions, but such details have not been measured. In this work, we developed correlated vibrational spectroscopy, a symmetry-based method that separates interacting from noninteracting molecules in self- and cross-correlation spectra, giving access to previously inaccessible information. We found that hydroxide (OH-) donated similar to 8% more negative charge to the H bond network of water, and hydronium (H3O+) accepted similar to 4% less negative charge from the H bond network of water. Deuterium oxide (D2O) had similar to 9% more H bonds compared with water (H2O), and acidic solutions displayed more dominant NQEs than basic ones.