Halide Ion Microhydration: Structure, Energetics, and Spectroscopy of Small Halide–Water Clusters
Replica exchange molecular dynamics simulations and vibrational spectroscopy calculations are performed using halide–water many-body potential energy functions to provide a bottom-up analysis of the structures, energetics, and hydrogen-bonding arrangements in X–(H2O) n (n = 3–6) clusters, with X = F...
Saved in:
| Published in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 123; no. 13; pp. 2843 - 2852 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
American Chemical Society
04-04-2019
|
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Summary: | Replica exchange molecular dynamics simulations and vibrational spectroscopy calculations are performed using halide–water many-body potential energy functions to provide a bottom-up analysis of the structures, energetics, and hydrogen-bonding arrangements in X–(H2O) n (n = 3–6) clusters, with X = F, Cl, Br, and I. Independently of the cluster size, it is found that all four halides prefer surface-type structures in which they occupy one of the vertices in the underlying three-dimensional hydrogen-bond networks. For fluoride–water clusters, this is in contrast to previous reports suggesting that fluoride prefers interior-type arrangements, where the ion is fully hydrated. These differences can be ascribed to the variability in how various molecular models are capable of reproducing the subtle interplay between halide–water and water–water interactions. Our results thus emphasize the importance of a correct representation of individual many-body contributions to the molecular interactions for a quantitative description of halide ion hydration. |
|---|---|
| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1089-5639 1520-5215 |
| DOI: | 10.1021/acs.jpca.9b00816 |