Issue 42, 2014

Where does the Raman optical activity of [Rh(en)3]3+ come from? Insight from a combined experimental and theoretical approach

Abstract

Backscattered Raman optical activity (ROA) spectra are measured for Δ- and Λ-tris-(ethylenediamine)rhodium(III) chloride in aqueous solution. In addition, the spectra of the four possible conformers in the Λ configuration are investigated by ab initio calculations. The Λ(δδδ) conformer is in best agreement with experimental spectra and examined in more details. The two most stable conformers according to the calculations are not compatible with the experimental ROA spectrum. Insights into the origin of observed band intensities are obtained by means of group coupling matrices. The influence of the first solvation shell is explored via an ab initio molecular dynamics simulation. Taking explicit solvent molecules into account further improves the agreement between calculation and experiment. Analysis of selected normal modes using group coupling matrices shows that solvent molecules lead to normal mode rotation and thus contribute to the ROA intensity, whereas the contribution of the Rh can be neglected.

Graphical abstract: Where does the Raman optical activity of [Rh(en)3]3+ come from? Insight from a combined experimental and theoretical approach

Supplementary files

Article information

Article type
Paper
Submitted
16 May 2014
Accepted
15 Sep 2014
First published
18 Sep 2014

Phys. Chem. Chem. Phys., 2014,16, 23260-23273

Author version available

Where does the Raman optical activity of [Rh(en)3]3+ come from? Insight from a combined experimental and theoretical approach

M. Humbert-Droz, P. Oulevey, L. M. Lawson Daku, S. Luber, H. Hagemann and T. Bürgi, Phys. Chem. Chem. Phys., 2014, 16, 23260 DOI: 10.1039/C4CP02145B

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