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Lack of evidence for phase-only control of retinal photoisomerization in the strict one-photon limit

Nature Chemistry volume 9, pages 45–49 (2017)Cite this article

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Abstract

The concept of shaping electric fields to steer light-induced processes coherently has fascinated scientists for decades. Despite early theoretical considerations that ruled out one-photon coherent control (CC), several experimental studies reported that molecular responses are sensitive to the shape of the excitation field in the weak-field limit. These observations were largely attributed to the presence of rapid-decay channels, but experimental verification is lacking. Here, we test this hypothesis by investigating the degree of achievable control over the photoisomerization of the retinal protonated Schiff-base in bacteriorhodopsin, isorhodopsin and rhodopsin, all of which exhibit similar chromophores but different isomerization yields and excited-state lifetimes. Irrespective of the system studied, we find no evidence for dissipation-dependent behaviour, nor for any CC in the strict one-photon limit. Our results question the extent to which a photochemical process at ambient conditions can be controlled at the amplitude level, and how the underlying molecular potential-energy surfaces and dynamics may influence this controllability.

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Figure 1: Concept and realization of the self-referenced weak-field CC experiment.
Figure 2: Self-referenced CC of rho101 under high- and weak-field conditions.
Figure 3: Weak-field CC on retinal protonated Schiff-bases embedded in different opsin proteins.

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Acknowledgements

We thank K. M. Spillane, G. Bassolino, G. F. Taylor and A. Watts for the rhodopsin, isorhodopsin and bacteriorhodopsin samples. This work was supported by a Career Acceleration Fellowship from the Engineering and Physical Sciences Research Council (EP/H003541/1).

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  1. M. Liebel

    Present address: Present address: ICFO-Institut de Ciencies Fotoniques, The Barcelona Institute of Science and Technology, 08860 Castelldefels (Barcelona), Spain,

Authors and Affiliations

  1. Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QZ, UK

    M. Liebel & P. Kukura

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  1. M. Liebel
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Contributions

P.K. proposed the project, P.K. and M.L. designed the experiments, M.L. performed the experiments and P.K. and M.L. analysed and discussed the data and wrote the manuscript together.

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Correspondence to P. Kukura.

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Liebel, M., Kukura, P. Lack of evidence for phase-only control of retinal photoisomerization in the strict one-photon limit. Nature Chem 9, 45–49 (2017). https://doi.org/10.1038/nchem.2598

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