Work

Opposing Electronic and Nuclear Quantum Effects on Hydrogen Bonds in H 2 O and D 2 O

Year: 2019

Type: article

Abstract: 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 σ‐hole to form on hydrogen atoms is strengthened when the bond is stretched, so that the σ‐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 H 2 O relative to D 2 O, whereas nuclear quantum effects weaken it. These quantum fluctuations are stronger for the water dimer than in bulk water.

Source: ChemPhysChem

DOI: 10.1002/cphc.201900839

Authors: Timothy Clark, Julian Heske, Thomas D. Kühne

Institutions: Friedrich-Alexander-Universität Erlangen-Nürnberg, Paderborn University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $3,500

Funders: European Commission, Deutsche Forschungsgemeinschaft