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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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).
The authors declare no competing financial interests.
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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