期刊
CHEMPHYSCHEM
卷 20, 期 19, 页码 2461-2465出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201900839
关键词
ab initio calculations; bond theory; hydrogen bonds; isotope effects; solvent effects
资金
- Deutsche Forschungsgemeinschaft as part of the Excellence Cluster Engineering of Advanced Materials
- European Research Council (ERC) under the European Union [716142]
The effect of extending the O-H bond length(s) in water on the hydrogen-bonding strength has been investigated using static ab initio molecular orbital calculations. The polar flattening effect that causes a slight sigma-hole to form on hydrogen atoms is strengthened when the bond is stretched, so that the sigma-hole becomes more positive and hydrogen bonding stronger. In opposition to this electronic effect, path-integral ab initio molecular-dynamics simulations show that the nuclear quantum effect weakens the hydrogen bond in the water dimer. Thus, static electronic effects strengthen the hydrogen bond in H2O relative to D2O, whereas nuclear quantum effects weaken it. These quantum fluctuations are stronger for the water dimer than in bulk water.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据