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Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent

Nature Chemistry volume 8, pages 1042–1046 (2016)Cite this article

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Abstract

Spectroscopically observing the translational and rotational motion of solute molecules in liquid solutions is typically impeded by their interactions with the solvent, which conceal spectral detail through linewidth broadening. Here we show that unique insights into solute dynamics can be made with perfluorinated solvents, which interact weakly with solutes and provide a simplified liquid environment that helps to bridge the gap in our understanding of gas- and liquid-phase dynamics. Specifically, we show that in such solvents, the translational and rotational cooling of an energetic CN radical can be observed directly using ultrafast transient absorption spectroscopy. We observe that translational-energy dissipation within these liquids can be modelled through a series of classic collisions, whereas classically simulated rotational-energy dissipation is shown to be distinctly faster than experimentally measured. We also observe the onset of rotational hindering from nearby solvent molecules, which arises as the average rotational energy of the solute falls below the effective barrier to rotation induced by the solvent.

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Figure 1: Transient electronic absorption spectra that result from gas-phase BrCN photolysis at 220 nm.
Figure 2: Transient electronic absorption spectra that result from solution-phase BrCN photolysis at 220 nm.
Figure 3: Interpretation of transient spectra from Fig. 2.
Figure 4: Kinetic traces of translational- and rotational-energy relaxation.

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Acknowledgements

We thank the European Research Council for the award of Advanced Grant 290966 CAPRI. M.P.G. is supported by a Marie Curie International Incoming Fellowship (PIIF-GA-2012-326988).

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Authors and Affiliations

  1. School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK

    Michael P. Grubb, Philip M. Coulter, Hugo J. B. Marroux, Balazs Hornung, Ryan S. McMullen, Andrew J. Orr-Ewing & Michael N. R. Ashfold

  2. Department of Chemistry, Fort Lewis College, Durango, 81301, Colorado, USA

    Michael P. Grubb

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Contributions

M.P.G., A.J.O.E. and M.N.R.A. conceived the study. M.P.G., P.M.C. and R.S.M. planned and performed the liquid-phase transient experiments. H.J.B.M. planned and performed the transient gas-phase experiments. M.P.G. and P.M.C. analysed the data and conceived the theoretical models. B.H. performed the MD simulations. M.P.G., A.J.O.E. and M.N.R.A. wrote the paper with input from all the authors.

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Correspondence to Michael P. Grubb.

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Grubb, M., Coulter, P., Marroux, H. et al. Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent. Nature Chem 8, 1042–1046 (2016). https://doi.org/10.1038/nchem.2570

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