Issue 6, 2015

Reactivity of aldehydes at the air–water interface. Insights from molecular dynamics simulations and ab initio calculations

Abstract

Understanding the influence of solute–solvent interactions on chemical reactivity has been a subject of intense research in the last few decades. Theoretical studies have focused on bulk solvation phenomena and a variety of models and methods have been developed that are now widely used by both theoreticians and experimentalists. Much less attention has been paid, however, to processes that occur at liquid interfaces despite the important role such interfaces play in chemistry and biology. In this study, we have carried out sequential molecular dynamics simulations and quantum mechanical calculations to analyse the influence of the air–water interface on the reactivity of formaldehyde, acetaldehyde and benzaldehyde, three simple aldehydes of atmospheric interest. The calculated free-energy profiles exhibit a minimum at the interface, where the average reactivity indices may display large solvation effects. The study emphasizes the role of solvation dynamics, which are responsible for large fluctuations of some molecular properties. We also show that the photolysis rate constant of benzaldehyde in the range 290–308 nm increases by one order of magnitude at the surface of a water droplet, from 2.7 × 10−5 s−1 in the gas phase to 2.8 × 10−4 s−1 at the air–water interface, and we discuss the potential impact of this result on the chemistry of the troposphere. Experimental data in this domain are still scarce and computer simulations like those presented in this work may provide some insights that can be useful to design new experiments.

Graphical abstract: Reactivity of aldehydes at the air–water interface. Insights from molecular dynamics simulations and ab initio calculations

Article information

Article type
Paper
Submitted
23 九月 2014
Accepted
25 十一月 2014
First published
25 十一月 2014

Org. Biomol. Chem., 2015,13, 1673-1679

Reactivity of aldehydes at the air–water interface. Insights from molecular dynamics simulations and ab initio calculations

M. T. C. Martins-Costa, F. F. García-Prieto and M. F. Ruiz-López, Org. Biomol. Chem., 2015, 13, 1673 DOI: 10.1039/C4OB02029D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements